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Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal-covalent organic frameworks (MCOFs) with both small-sized metal clusters and nitrogen-rich ligands, named COF-Cu 3 TG. Based on our design, small-sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen-rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single-atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N 2 -Ru-N 2 electron bridge (Ru-SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g -1  h -1 . Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru-SAEB were reasonably inferred, further confirming the rationality of the Ru-SAEB configuration. A sufficiently proximity between the small-sized Cu 3 cluster and the Ru-SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru-SAEB for efficient photocatalytic hydrogen production., (© 2024 Wiley-VCH GmbH.)

Objective: This study aimed to analyze the demographic characteristics, symptoms, and treatment outcomes of patients diagnosed with May-Thurner syndrome (MTS) using computed tomography venography (CTV)., Methods: Medical records of patients diagnosed with MTS through CTV at Hebei General Hospital of China between April 1, 2017, and May 31, 2022, were reviewed. The data collected included: (1) gender, age, body mass index (BMI), and smoking and drinking habits; (2) time of onset and symptoms of MTS, as well as other accompanying symptoms; (3) additional diagnoses, length of hospital stay (days), treatment methods, treatment success, and the occurrence of post-treatment bleeding or recurrence. Descriptive statistics were used, with mean ± standard deviation and median values reported. The t-test/u-test and Chi-square test (including the exact probability method) were used to compare means and rates, respectively, with a significance level set at α = 0.05., Results: Out of 402 patients (233 males, 169 females), 118 (29.4%) were diagnosed with MTS, with 47 (21.1%) males and 71 (39.7%) females. The incidence of MTS was significantly higher in females than males (χ 2 proportion = 16.545, χ 2 composition = 9.763, p  < 0.05). The average ages of male and female MTS patients were 56.4 and 59.9 years, respectively, with mean BMIs of 27.05 and 27.09 kg/m 2 . Among male patients, 27.7% (13) were smokers, and 17.0% (8) consumed alcohol. Inferior vena cava (IVC) thrombosis was notable in 59.3% of MTS patients, with a significantly higher proportion in females (70.4%) than in males (42.6%) (χ 2 = 9.102, p  < 0.05). Lower limb swelling without pain was reported by 70.3% of patients, with 53.4% (44.7% male, 59.2% female) experiencing swelling on the left side only, which was significantly more common than swelling on the right side only or both sides (χ 2 = 44.554, p  < 0.05). Additionally, 12.7% of patients reported both swelling and pain, with left-side symptoms being more prevalent than right-side or both sides. The average ages at symptom onset were 51.3 ± 17.1 years in males and 57.1 ± 13.2 years in females. All treatments for MTS were successful without bleeding or recurrence. The most common treatment method was balloon dilation combined with stent placement (57.6%)., Conclusion: CTV is highly effective in detecting and facilitating the successful treatment of MTS. It should be fully utilized to promote early diagnosis and treatment of MTS. Female MTS patients need more medical resources for diagnosis and treatment.

The applications of indirect electrocatalysis toward potential industrial processes are drastically limited by the utilization or processing forms of electrocatalysts. The remaining challenges of electrocatalysts like the recycling in homogeneous systems or pulverization in heterogeneous systems call for advanced processing forms to meet the desired requirements. Here, we report a series of metalloporphyrin-based polymer fibers (M-PF, M = Ni, Cu and Zn) through a rigid-flexible polymerization strategy based on rigid metalloporphyrin and flexible thiourea units that can be applied as heterogenous redox-mediators in indirect electrocatalysis. These functional fibers with high strength and flexibility exhibit interweavable and designable functions that can be processed into different fiber-forms like knotted, two-spiral, three-ply, five-ply fibers or even interweaved networks. Interestingly, they can be readily applied in S-S bond cleaving/cyclization reaction or extended oxidative self-coupling reaction of thiols with high efficiency. Remarkably, it enables the scale-up production (1.25 g in a batch-experiment) under laboratory conditions., (© 2024 Wiley‐VCH GmbH.)

The multiple mortise-and-tenon joint parts are the core factors to provide the structural stability and diversity of Chinese Luban locks; however, constructing such structures is very challenging. Herein, single crystals of a covalent organic nanoribbon (named CityU-27) are prepared through the assembly of hexahydroxytriphenylene (HHTP), 4,4'-vinylenedipyridine (BYE), and phenylboronic acid (BA) together through dative boron←nitrogen (B←N) bonds. The single-crystal X-ray diffraction analysis indicates that CityU-27 has a covalent organic nanoribbon structure, where each nanoribbon forms multiple and tight π-π interactions with four neighboring others to generate a Luban lock-like configuration. CityU-27 has been demonstrated to be an efficient photocatalyst in a one-pot tandem reaction of hydrogen evolution reaction (HER) and semi-hydrogenation reaction of alkynes in series to produce olefins without any additional photosensitizers and co-catalysts (metal-free)., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Rational design of robust photocatalytic systems to direct capture and in-situ convert diluted CO 2 from flue gas is a promising but challenging way to achieve carbon neutrality. Here, we report a new type of host-guest photocatalysts by integrating CO 2 -enriching ionic liquids and photoactive metal-organic frameworks PCN-250-Fe 2 M (M = Fe, Co, Ni, Zn, Mn) for artificial photosynthetic diluted CO 2 reduction in gas-solid phase. As a result, [Emim]BF 4 (39.3 wt%)@PCN-250-Fe 2 Co exhibits a record high CO 2 -to-CO reduction rate of 313.34 μmol g -1 h -1 under pure CO 2 atmosphere and 153.42 μmol g -1 h -1 under diluted CO 2 (15%) with about 100% selectivity. In scaled-up experiments with 1.0 g catalyst and natural sunlight irradiation, the concentration of pure and diluted CO 2 (15%) could be significantly decreased to below 85% and 10%, respectively, indicating its industrial application potential. Further experiments and theoretical calculations reveal that ionic liquids not only benefit CO 2 enrichment, but also form synergistic effect with Co 2+ sites in PCN-250-Fe 2 Co, resulting in a significant reduction in Gibbs energy barrier during the rate-determining step of CO 2 -to-CO conversion., (© 2024. The Author(s).)

Significant efforts have been devoted to removal and recycling of microplastics (MPs; <5 mm) to address the environmental crises caused by their ubiquitous presence and improper treatment. Metal-organic frameworks (MOFs) demonstrate compatibility with MPs/plastics through adsorption, degradation, or assembly with the MPs/plastic polymers. Above 90% of MPs/plastic particles can be adsorbed on MOF materials via the hydrophobic interaction, electrical attraction, π-π stacking, and van der Waals forces. Meanwhile, certain MOFs have successfully converted various types of plastics into high-valued small molecules through thermocatalysis and photocatalysis. In thermocatalysis, the primary process should be C-O bond cleavage, whereas in photocatalysis it ought to be the generation of reactive oxygen species (ROS). Moreover, the construction of novel MOFs using waste MPs/plastics as the ligands was mostly accomplished through three dominant ways, including glycolysis, hydrolysis and methanolysis. Once successfully composited, the MOF@plastic materials illustrated tremendous promise for interdisciplinary research in multifunctional applications, including sewage treatment, gas adsorption/separation, and the preparation of microbial fuel cells, plastic scintillators and other sensors. The review explicated the relationships between MPs/plastics and MOF materials, as well as the challenges and perspectives for their development. It can provide a deeper understanding of how MOFs remove/degrade MP/plastic particles, how MPs/plastics are recycled to prepare MOFs, and how to build multifunctional MOF@plastic composites. Overall, this analysis is anticipated to outline future prospects for turning the threats (MPs/plastics contamination) into opportunities ( e.g. , as ligands to prepare MOF or MOF@plastic materials for further applications)., Competing Interests: The authors declare they have no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Directly converting CO 2 in flue gas using artificial photosynthetic technology represents a promising green approach for CO 2 resource utilization. However, it remains a great challenge to achieve efficient reduction of CO 2 from flue gas due to the decreased activity of photocatalysts in diluted CO 2 atmosphere. Herein, we designed and synthesized a series of dual metallosalen-based covalent organic frameworks (MM-Salen-COFs, M: Zn, Ni, Cu) for artificial photosynthetic diluted CO 2 reduction and confirmed their advantage in comparison to that of single metal M-Salen-COFs. As a results, the ZnZn-Salen-COF with dual Zn sites exhibits a prominent visible-light-driven CO 2 -to-CO conversion rate of 150.9 μmol g -1  h -1 under pure CO 2 atmosphere, which is ~6 times higher than that of single metal Zn-Salen-COF. Notably, the dual metal ZnZn-Salen-COF still displays efficient CO 2 conversion activity of 102.1 μmol g -1  h -1 under diluted CO 2 atmosphere from simulated flue gas conditions (15 % CO 2 ), which is a record high activity among COFs- and MOFs-based photocatalysts under the same reaction conditions. Further investigations and theoretical calculations suggest that the synergistic effect between the neighboring dual metal sites in the ZnZn-Salen-COF facilitates low concentration CO 2 adsorption and activation, thereby lowering the energy barrier of the rate-determining step., (© 2024 Wiley-VCH GmbH.)

The design of efficient heterogeneous redox mediators with favorable affinity to substrate and electrolyte are much desired yet still challenging for the development of indirect electrolysis system. Herein, for the first time, we have developed a solid-liquid-gas three-phase indirect electrolysis system based on a covalent organic framework (Dha-COF-Cu) as heterogeneous redox mediator for S-S coupling reaction. Dha-COF-Cu with the integration of high porosity, nanorod morphology, abundant hydroxyl groups and active Cu sites is much beneficial for the adsorption/activation of thiols, uniform dispersion and high wettability in electrolyte, and efficient interfacial electron transfer. Notably, Dha-COF-Cu as solid-phase redox mediator exhibits excellent electrocatalytic efficiency for the formation of value-added liquid-phase S-S bond product (yields up to 99 %) coupling with the generation of gas-phase product of H 2 (~1.40 mmol g -1  h -1 ), resulting in a powerful three-phase indirect electrolysis system. This is the first work about COFs that can be applied in three-phase indirect electrolysis system, which might promote the development of porous crystalline materials in this field., (© 2024 Wiley-VCH GmbH.)

The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher connectivity remains a great challenge in the field of COF structural design. Herein, this work reports a hierarchical expansion strategy for making 16-connected building blocks to construct 3D COFs with sqc topology. The [16 + 2] construction achieved by condensation between a 16-connected carbazolyl dicyanobenzene-based building block (CzTPN) and linear diamino linkers (BD or Bpy) affords two 3D COFs (named CzBD COF and CzBpy COF). Furthermore, attributed to the well-organized donor-acceptor (D-A) heterojunction, the Ni chelated CzBpy COF (Ni@CzBpy COF) exhibits excellent performance for photoredox/Ni dual catalytic C(sp 3 )-C(sp 2 ) cross-coupling of alkyltrifluoroborates with aryl halides, achieving a maximum 98% conversion and 94% yield for various substrates. This work developed the first case of high-connectivity COFs bearing 16-connected units, which is the highest connectivity reported until now, and achieved efficient photocatalysis applications, thus greatly enriching the possibilities of COFs.

Single-particle analysis (SPA) is a fundamental method of cryo-electron microscopy developed to resolve the structures of biological macromolecules. This method has seen significant success in structural biology, yet its potential applications in synthetic chemical systems remain underexplored. In this perspective article, SPA and associated electron microscopy techniques are first briefly introduced. It is then proposed that SPA is well-suited for structural analysis of chemical systems where discrete, identical macromolecules can be readily obtained. Applicable systems include various clusters such as coinage metal clusters, metal-oxo/sulfur clusters, metal-organic clusters, and supramolecular compounds like coordination cages and metallo-supramolecular cages. When high-quality large single crystals are unattainable, SPA provides an alternative method for determining their structures. Beyond these end products, it is suggested that SPA can be instrumental in studying synthetic intermediates of materials with specific building units, such as metal-organic frameworks and zeolites. Given that various intermediates coexist in the reaction system, a purification step is necessary before conducting SPA, which can be facilitated by soft-landing electrospray ionization mass spectrometry., (© 2024 Wiley‐VCH GmbH.)

The construction of isotypic high-nuclearity inorganic cages with identical pristine parent structure and increasing nuclearity is highly important for molecular growth and structure-property relationship study, yet it still remains a great challenge. Here, we provide an in situ growth approach for successfully synthesizing a series of new giant hollow polymolybdate dodecahedral cages, Mo 250 , Mo 260 -I , and Mo 260 -E , whose structures are growth based on giant polymolybdate cage Mo 240 . Remarkably, they show two pathways of nuclear growth based on Mo 240 , that is, the growth of 10 and 20 Mo centers on the inner and outer surfaces to afford Mo 250 and Mo 260 -I , respectively, and the growth of 10 Mo centers both on the inner and outer surfaces to give Mo 260 -E . To the best of our knowledge, this is the first study to display the internal and external nuclear growth of a giant hollow polyoxometalate cage. More importantly, regular variations in structure and nuclearity confer these polymolybdate cages with different optical properties, oxidative activities, and hydrogen atom transfer effect, thus allowing them to exhibit moderate to excellent photocatalytic performance in oxidative cross-coupling reactions between different unactivated alkanes and N-heteroarenes. In particular, Mo 240 and Mo 260 -E with better comprehensive abilities can offer the desired coupling product with yield up to 92% within 1 h.

Porous crystalline conjugated macrocyclic materials (CMMs) possess high porosity, tunable structure/function and efficient charge transport ability owing to their planar macrocyclic conjugated π-electron system, which make them promising candidates for applications in energy storage. In this review, we thoroughly summarize the timely development of porous crystalline CMMs in energy storage related fields. Specifically, we summarize and discuss their structures and properties. In addition, their energy storage applications, such as lithium ion batteries, lithium sulfur batteries, sodium ion batteries, potassium ion batteries, Li-CO 2 batteries, Li-O 2 batteries, Zn-air batteries, supercapacitors and triboelectric nanogenerators, are also discussed. Finally, we present the existing challenges and future prospects. We hope this review will inspire the development of advanced energy storage materials based on porous crystalline CMMs.

Developing novel proton exchange membranes (PEMs) with low cost and superior performance to replace Nafion is of great significance. Polyoxometalate-doped sulfonated poly(aryl ether ketone sulfone) (SPAEKS) allows for the amalgamation of the advantages in each constituent, thereby achieving an optimized performance for the hybrid PEMs. Herein, the hybrid membranes by introducing 2MeIm-{Mo 132 } into SPAEKS are obtained. Excellent hydrophilic properties of 2MeIm-{Mo 132 } can help more water molecules be retained in the hybrid membrane, providing abundant carriers for proton transport and proton hopping sites to build successive hydrophilic channels, thus lowering the energy barrier, accelerating the proton migration, and significantly fostering the proton conductivity of hybrid membranes. Especially, SP-2MIMo 132 -5 exhibits an enhanced proton conductivity of 75 mS cm -1 at 80 °C, which is 82.9% higher than pristine SPAEKS membrane. Additionally, this membrane is suitable for application in proton exchange membrane fuel cells, and a maximum power density of 266.2 mW cm -2 can be achieved at 80 °C, which far exceeds that of pristine SPAEKS membrane (54.6 mW cm -2 ). This work demonstrates that polyoxometalate-based clusters can serve as excellent proton conduction sites, opening up the choice of proton conduction carriers in hybrid membrane design and providing a novel idea to manufacture high-performance PEMs., (© 2024 Wiley‐VCH GmbH.)

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th 12 L 3 -MA 12 , Th 12 L 3 -MA 6 -BF 6 , and Th 12 L 3 -Fcc 12 , which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H + , O 2 •- , or t BuO/ t BuOO • ) and activation of substrate molecules, thus achieving superior catalytic performance. This work is not only the first to develop radiation-resistant thorium cluster catalysts to perform efficient redox reactions but also provides design ideas for the construction of high-nuclearity thorium clusters under mild conditions.

Hydrazone-linked covalent organic frameworks (COFs) with structural flexibility, heteroatomic sites, post-modification ability and high hydrolytic stability have attracted great attention from scientific community. Hydrazone-linked COFs, as a subclass of Schiff-base COFs, was firstly reported in 2011 by Yaghi's group and later witnessed prosperous development in various aspects. Their adjustable structures, precise pore channels and plentiful heteroatomic sites of hydrazone-linked structures possess much potential in diverse applications, for example, adsorption/separation, chemical sensing, catalysis and energy storage, etc. Up to date, the systematic reviews about the reported hydrazone-linked COFs are still rare. Therefore, in this review, we will summarize their preparation methods, characteristics and related applications, and discuss the opportunity or challenge of hydrazone-linked COFs. We hope this review could provide new insights about hydrazone-linked COFs for exploring more appealing functions or applications., (© 2024 Wiley-VCH GmbH.)

A ferrocene-modified COF, namely Ni-Tph-COF-Fc, was synthesized and applied in OER. Compared with Ni-Tph-COF-OH, Ni-Tph-COF-Fc shows improved performance with a current density of 99.6 mA cm -2 , an overpotential of 450 mV, and a Tafel slope of 73.1 mV dec -1 , which may be attributed to a synergy between introduced ferrocene and metalloporphyrin in the COFs. Moreover, the enhanced OER performance leads to an improved CO 2 RR performance with an FE CO of 93.1%. This work represents an effective strategy to enhance the anodic OER performance and realize efficient CO 2 RR.

D-UiO-66-NIM with high proton conductivity has been synthesized through the dual strategy of defect engineering and ligand modification. Moreover, D-UiO-66-NIM exhibits good temperature cycling stability and durability in proton conductivity. This work has developed a new method to obtain efficient MOF-based proton conductors.

Ultra-low temperature resistant adhesive is highly desired yet scarce for material adhesion for the potential usage in Arctic/Antarctic or outer space exploration. Here we develop a solvent-free processed low-temperature tolerant adhesive with excellent adhesion strength and organic solvent stability, wide tolerable temperature range (i.e. -196 to 55 °C), long-lasting adhesion effect ( > 60 days, -196 °C) that exceeds the classic commercial hot melt adhesives. Furthermore, combine experimental results with theoretical calculations, the strong interaction energy between polyoxometalate and polymer is the main factor for the low-temperature tolerant adhesive, possessing enhanced cohesion strength, suppressed polymer crystallization and volumetric contraction. Notably, manufacturing at scale can be easily achieved by the facile scale-up solvent-free processing, showing much potential towards practical application in Arctic/Antarctic or planetary exploration., (© 2024. The Author(s).)

Visible-light sensitive and bi-functionally favored CO 2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization of ultraviolet light and improve sluggish kinetics is demanded to conquer the current technique-barrier of traditional Li-CO 2 battery. Here, a kind of redox molecular junction sp 2 c metal-covalent organic framework (i.e. Cu 3 -BTDE-COF) has been prepared through the connection between Cu 3 and BTDE and can serve as efficient photocathode catalyst in light-assisted Li-CO 2 battery. Cu 3 -BTDE-COF with redox-ability, visible-light-adsorption region, electron-hole separation ability and endows the photocathode with excellent round-trip efficiency (95.2 %) and an ultralow voltage hysteresis (0.18 V), outperforming the Schiff base COFs (i.e. Cu 3 -BTDA-COF and Cu 3 -DT-COF) and majority of the reported photocathode catalysts. Combined theoretical calculations with characterizations, Cu 3 -BTDE-COF with the integration of Cu 3 centers, thiazole and cyano groups possess strong CO 2 adsorption/activation and Li + interaction/diffusion ability to boost the CRR/CER kinetics and related battery property., (© 2024 Wiley-VCH GmbH.)

Precise design and tuning of Zn hopping/transfer sites with deeper understanding of the dendrite-formation mechanism is vital in artificial anode protective coating for aqueous Zn-ion batteries (AZIBs). Here, we probe into the role of anode-coating interfaces by designing a series of anhydride-based covalent organic frameworks (i.e., PI-DP-COF and PI-DT-COF) with specifically designed zigzag hopping sites and zincophilic anhydride groups that can serve as desired platforms to investigate the related Zn 2+ hopping/transfer behaviours as well as the interfacial interaction. Combining theoretical calculations with experiments, the ABC stacking models of these COFs endow the structures with specific zigzag sites along the 1D channel that can accelerate Zn 2+ transfer kinetics, lower surface-energy, homogenize ion-distribution or electric-filed. Attributed to these superiorities, thus-obtained optimal PI-DT-COF cells offer excellent cycling lifespan in both symmetric-cell (2000 cycles at 60 mA cm -2 ) and full-cell (1600 cycles at 2 A g -1 ), outperforming almost all the reported porous crystalline materials., (© 2024 Wiley-VCH GmbH.)

The Zr(IV) ions are easily hydrolyzed to form oxides, which severely limits the discovery of new structures and applications of Zr-based compounds. In this work, three ferrocene (Fc)-functionalized Zr-oxo clusters (ZrOCs), Zr 9 Fc 6 , Zr 10 Fc 6 and Zr 12 Fc 8 were synthesized through inhibiting the hydrolysis of Zr(IV) ions, which show increased nuclearity and regular structural variation. More importantly, these Fc-functionalized ZrOCs were used as heterogeneous catalysts for the transfer hydrogenation of levulinic acid (LA) and phenol oxidation reactions for the first time, and displayed outstanding catalytic activity. In particular, Zr 12 Fc 8 with the largest number of Zr active sites and Fc groups can achieve > 95% yield for LA-to-γ-valerolactone within 4 h (130 °C) and > 98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-p-benzoquinone within 30 min (80 °C), showing the best catalytic performance. Catalytic characterization combined with theory calculations reveal that in the Fc-functionalized ZrOCs, the Zr active sites could serve as substrate adsorption sites, while the Fc groups could act as hydrogen transfer reagent or Fenton reagent, and thus achieve effectively intramolecular metal-ligand synergistic catalysis. This work develops functionalized ZrOCs as catalysts for thermal-triggered redox reactions., (Copyright © 2024 Science China Press. Published by Elsevier B.V. All rights reserved.)

Covalent-organic frameworks (COFs) with photoinduced donor-acceptor (D-A) radical pairs show enhanced photocatalytic activity in principle. However, achieving long-lived charge separation in COFs proves challenging due to the rapid charge recombination. Here, we develop a novel strategy by combining [6 + 4] nodes to construct zyg -type 3D COFs, first reported in COF chemistry. This structure type exhibits a fused Olympic-rings-like shape, which provides a platform for stabilizing the photoinduced D-A radical pairs. The zyg -type COFs containing catalytically active moieties such as triphenylamine and phenothiazine (PTZ) show superior photocatalytic production rates of hydrogen peroxide (H 2 O 2 ). Significantly, the photochromic radical states of these COFs show up to 400% enhancement in photocatalytic activity compared to the parent states, achieving a remarkable H 2 O 2 synthesis rate of 3324 μmol g -1 h -1 , which makes the PTZ-COF one of the best crystalline porous photocatalysts in H 2 O 2 production. This work will shed light on the synthesis of efficient 3D COF photocatalysts built on topologies that can facilitate photogenerating D-A radical pairs for enhanced photocatalysis., (© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Nanofluidic membranes have demonstrated great potential in harvesting osmotic energy. However, the output power densities are usually hampered by insufficient membrane permselectivity. Herein, we design a polyoxometalates (POMs)-based nanofluidic plasmonic electron sponge membrane (PESM) for highly efficient osmotic energy conversion. Under light irradiation, hot electrons are generated on Au NPs surface and then transferred and stored in POMs electron sponges, while hot holes are consumed by water. The stored hot electrons in POMs increase the charge density and hydrophilicity of PESM, resulting in significantly improved permselectivity for high-performance osmotic energy conversion. In addition, the unique ionic current rectification (ICR) property of the prepared nanofluidic PESM inhibits ion concentration polarization effectively, which could further improve its permselectivity. Under light with 500-fold NaCl gradient, the maximum output power density of the prepared PESM reaches 70.4 W m -2 , which is further enhanced even to 102.1 W m -2 by changing the ligand to P 5 W 30 . This work highlights the crucial roles of plasmonic electron sponge for tailoring the surface charge, modulating ion transport dynamics, and improving the performance of nanofluidic osmotic energy conversion., (© 2024. The Author(s).)

Although photocatalytic C-H activation has been realized by using heterogeneous catalysts, most of them require high-temperature conditions to provide the energy required for C-H bond breakage. The catalysts with photothermal conversion properties can catalyze this reaction efficiently at room temperature, but so far, these catalysts have been rarely developed. Here, we construct bifunctional catalysts Rh-COF-316 and -318 to combine photosensitive covalent organic frameworks (COFs) and transition-metal catalytic moiety using a post-synthetic approach. The Rh-COF enable the heterogeneous C-H activation reaction by photothermal conversion for the first time, and exhibit excellent yields (up to 98 %) and broad scope of substrates in [4+2] annulation at room temperature, while maintaining the high stability and recyclability. Significantly, this work is the highest yield reported so far in porous materials catalyzing C(sp 2 )-C(sp 2 ) formation at room temperature. The excellent performances can be attributed to the COF-316, which enhances the photothermal effect (ΔT=50.9 °C), thus accelerating C-H bond activation and the exchange of catalyst with substrates., (© 2024 Wiley‐VCH GmbH.)

Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal-organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu 3 } cluster-based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO 2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co-catalysts by one-step work-up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner., (© 2024 Wiley‐VCH GmbH.)

ConspectusTo cope with the increasingly global greenhouse effect and energy shortage, it is urgent to develop a feasible means to convert anthropogenic excess carbon dioxide (CO 2 ) into energy resources. The photocatalytic CO 2 reduction reaction (CO 2 RR) coupled with the water oxidation reaction (WOR), known as artificial photosynthesis, is a green, clean, and promoting strategy to deal with the above issues. Among the reported photocatalytic systems for CO 2 reduction, the main challenge is to achieve WOR simultaneously due to the limited charge separation efficiency and complicated dynamic process. To address the problem, scientists have assembled two nanosemiconductor motifs for CO 2 RR and WOR into a heterojunction photocatalyst to realize artificial photosynthesis. However, it is difficult to clearly explore the corresponding catalytic mechanism and establish an accurate structure-activity relationship at the molecular level for their aperiodic distribution and complicated structural information. Standing on the shoulders of the heterojunction photocatalysts, a new-generation material, hetero-motif molecular junction (HMMJ) photocatalysts, has been developed and studied by our laboratory. A hetero-motif molecular junction is a class of crystalline materials with a well-defined and periodic structure, adjustable assembly mode, and semiconductor-like properties, which is composed of two predesigned motifs with oxidation and reduction, respectively, by coordination or covalent bonds. The intrinsic properties make these catalysts susceptible to functional modifications to improve light absorption and electrical conductivity. The small size and short distance of the motifs can greatly promote the efficiency of photogenerated electron-hole separation and migration. Based on these advantages, they can be used as potential excellent photocatalysts for artificial photosynthesis. Notably, the explicit structural information determined by single-crystal or powder X-ray diffraction can provide a visual platform to explore the reaction mechanism. More importantly, the connection number, spatial distance, interaction, and arrangement mode of the structural motifs can be well-designed to explore the detailed structure-activity relationship that can be hardly studied in nanoheterojunction photocatalyst systems. In this regard, HMMJ photocatalysts can be a new frontier in artificial photosynthesis and serve as an important bridge between molecular photocatalysts and solid photocatalysts. Thus, it is very important to summarize the state-of-the-art of the HMMJ photocatalysts used for artificial photosynthesis and to give in-depth insight to promote future development.In this Account, we have summarized the recent advances in artificial photosynthesis using HMMJ photocatalysts, mainly focusing on the results in our lab. We present an overview of current knowledge about developed photocatalytic systems for artificial photosynthesis, introduce the design schemes of the HMMJ photocatalysts and their unique advantages as compared to other photocatalysts, summarize the construction strategies of HMMJ photocatalysts and their application in artificial photosynthesis, and explain why hetero-motif molecular junctions can be promising photocatalysts and show that they provide a powerful platform for studying photocatalysis. The structure-activity relationship and charge separation dynamics are illustrated. Finally, we bring our outlook on present challenges and future development of HMMJ photocatalysts and their potential application prospects on other photocatalytic reaction systems. We believe that this Account will afford important insights for the construction of high-efficiency photocatalysts and guidance for the development of more photocatalytic systems in an atom-economic, environmentally friendly, and sustainable way.

The striking aesthetic appeal of fullerene-like clusters has captured the interest of researchers. Nevertheless, the assembly of fullerene-like polyoxovadanadate (POV) cages remains a significant challenge due to the scarcity of suitable pentagonal motif. Herein, we have successfully synthesized the first fullerene-like all-inorganic POV cage, {(V 2 O)V 30 Nb 12 O 102 (H 2 O) 12 } (V 30 Nb 12 ), by introducing Nb into the POVs. V 30 Nb 12 is assembled by 12 heterometallic {(Nb)V 5 } pentagons through sharing V centers with I h symmetry, reminiscent of C 60 . To our knowledge, the fullerene-like V 30 Nb 12 not only represents the highest-nuclearity POV cage but also stands as the first niobovanadate cluster. Notably, V 30 Nb 12 exhibits excellent solution stability, as confirmed by ESI-MS, FT-IR and UV/Vis spectra. As there is no protection organic ligand on its outer surface, V 30 Nb 12 can be further modified with Cu-complexes to form a fullerene-like cluster based zigzag chain (Cu-V 30 Nb 12 )., (© 2024 Wiley-VCH GmbH.)

The electrochemical reduction of carbon dioxide (CO 2 ) to ethylene creates a carbon-neutral approach to converting carbon dioxide into intermittent renewable electricity. Exploring efficient electrocatalysts with potentially high ethylene selectivity is extremely desirable, but still challenging. In this report, a laboratory-designed catalyst HKUST-1@Cu 2 O/PTFE-1 is prepared, in which the high specific surface area of the composites with improved CO 2 adsorption and the abundance of active sites contribute to the increased electrocatalytic activity. Furthermore, the hydrophobic interface constructed by the hydrophobic material polytetrafluoroethylene (PTFE) effectively inhibits the occurrence of hydrogen evolution reactions, providing a significant improvement in the efficiency of CO 2 electroreduction. The distinctive structures result in the remarkable hydrocarbon fuels generation with high Faraday efficiency (FE) of 67.41%, particularly for ethylene with FE of 46.08% (-1.0 V vs RHE). The superior performance of the catalyst is verified by DFT calculation with lower Gibbs free energy of the intermediate interactions with improved proton migration and selectivity to emerge the polycarbon（C 2+ ） product. In this work, a promising and effective strategy is presented to configure MOF-based materials with tailored hydrophobic interface, high adsorption selectivity and more exposed active sites for enhancing the efficiency of the electroreduction of CO 2 to C 2+ products with high added value., (© 2023 Wiley‐VCH GmbH.)

Effective personal protection is crucial for controlling infectious disease spread. However, commonly used personal protective materials such as disposable masks lack antibacterial/antiviral function and may lead to cross infection. Herein, a polyethylene glycol-assisted solvent-free strategy is proposed to rapidly synthesize a series of the donor-acceptor metal-covalent organic frameworks (MCOFs) (i.e., GZHMU-2, JNM-1, and JNM-2) under air atmosphere and henceforth extend it via in situ hot-pressing process to prepare MCOFs based films with photocatalytic disinfect ability. Best of them, the newly designed GZHMU-2 has a wide absorption spectrum (200 to 1500 nm) and can efficiently produce reactive oxygen species under sunlight irradiation, achieving excellent photocatalytic disinfection performance. After in situ hot-pressing as a film material, the obtained GZHMU-2/NMF can effectively kill E. coli (99.99%), S. aureus (99%), and H1N1 (92.5%), meanwhile possessing good reusability. Noteworthy, the long-term use of a GZHMU-2/NWF-based mask has verified no damage to the living body by measuring the expression of mouse blood routine, lung tissue, and inflammatory factors at the in-vivo level., (© 2023 Wiley‐VCH GmbH.)

The performance applications (e.g., photocatalysis) of zirconium (Zr) and hafnium (Hf) based complexes are greatly hindered by the limited development of their structures and the relatively inert metal reactivity. In this work, we constructed two ultrastable Zr/Hf-based clusters (Zr 9 -TC4A and Hf 9 -TC4A) using hydrophobic 4-tert-butylthiacalix[4]arene (H 4 TC4A) ligands, in which unsaturated coordinated sulfur (S) atoms on the TC4A 4- ligand can generate strong metal-ligand synergy with nearby active metal Zr/Hf sites. As a result, these two functionalized H 4 TC4A ligands modified Zr/Hf-oxo clusters, as catalysts for the amine oxidation reaction, exhibited excellent catalytic activity, achieving very high substrate conversion (>99%) and product selectivity (>90%). Combining comparative experiments and theoretical calculations, we found that these Zr/Hf-based cluster catalysts accomplish efficient amine oxidation reactions through synergistic effect between metals and ligands: (i) The photocatalytic benzylamine (BA) oxidation reaction was achieved by the synergistic effect of the dual active sites, in which, the naked S sites on the TC4A 4- ligand oxidize the BA by photogenerated hole and oxygen molecules are reduced by photogenerated electrons on the metal active sites; (ii) in the aniline oxidation reaction, aniline was adsorbed by the bare S sites on ligands to be closer to metal active sites and then oxidized by the oxygen-containing radicals activated by the metal sites, thus completing the catalytic reaction under the synergistic catalytic effect of the proximity metal-ligand. In this work, the Zr/Hf-based complexes applied in the oxidation of organic amines have been realized using active S atom-directed metal-ligand synergistic catalysis and have demonstrated very high reactivity., Competing Interests: Conflict of interest The authors declare that they have no conflict of interest., (Copyright © 2023 Science China Press. Published by Elsevier B.V. All rights reserved.)

Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction of functional groups, have aroused broad interest in the field of photocatalysis. However, due to the low light absorption intensity, low photoelectron conversion efficiency, and lack of suitable active sites, it remains a great challenge to achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed a series of three-motif molecular junction type COFs, which formed dual photosensitizer coupled redox molecular junctions containing multifunctional COF photocatalysts. Significantly, due to the strong light adsorption ability of dual photosensitizer units and integrated oxidation and reduction features, the PY-BT COF exhibited the highest activity for photocatalytic aerobic oxidation. Especially, it achieved a photocatalytic benzylamine conversion efficiency of 99.9% in 2.5 h, which is much higher than that of the two-motif molecular junctions with only one photosensitizer or redox unit lacking COFs. The mechanism of selective aerobic oxidation was studied through comprehensive experiments and density functional theory calculations. The results showed that the photoinduced electron transfer occurred from PY and then through triphenylamine to BT. Furthermore, the thermodynamics energy for benzylamine oxidation on PY-BT COF was much lower than that for others, which confirmed the synergistic effect of dual photosensitizer coupled redox molecular junction COFs. This work provided a new strategy for the design of functional COFs with three-motif molecular junctions and also represented a new insight into the multifunctional COFs for organic catalytic reactions.

In modern industries, the aerobic oxidation of C(sp 3 )-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O 2 and oxidation of C(sp 3 )-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp 3 )-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat -1 ) is observed. In addition to the direct oxidation of C(sp 3 )-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications., (© 2024. The Author(s).)

Spin-state transition is a vital factor that dominates catalytic processes, but unveiling its mechanism still faces the great challenge of the lack of catalyst model systems. Herein, we propose that the {Fe-Pt} Hofmann clathrates, whose dynamic spin-state transition of metal centers can be chemically manipulated through iodine treatment, can serve as model systems in the spin-related structural-catalytic relationship study. Taking the photocatalytic synthesis of H 2 O 2 as the basic catalytic reaction, when the spin state of Fe(II) in the clathrate is high spin (HS), sacrificial agents are indispensable to the photosynthesis of H 2 O 2 because only the photocatalytic oxygen reduction reaction (ORR) occurs; when it is low spin (LS), both the ORR and water oxidation reaction (WOR) can take place, enabling a high H 2 O 2 photosynthesis rate of 66 000 μM g -1 h -1 under visible-light irradiation. In situ characterizations combined with density functional theory calculations confirmed that, compared with the HS-state counterpart, the LS state can induce strong charge transfer between the LS Fe(II) and the iodide-coordinating Pt(IV) in the polymer and reduce the energy barriers for both the ORR and WOR processes, dominating the on-off switching upon the photosynthesis of H 2 O 2 in O 2 -saturated water. What's more, the one-pot tandem reactions were conducted to utilize the synthesized H 2 O 2 for transforming the low-value-added sodium alkenesulfonates into value-added bromohydrin products with decent conversion rates. This work provides a pioneering investigation into on-off switching the photocatalytic overall reaction through manipulating the metallic spin-state transition in spin-crossover systems.

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO 2 photoreduction reaction. However, the systematic studies on the structure-functional relationship regarding the above two factors based on precisely structure model are rarely reported. Herein, as a proof-of-concept, we developed a new strategy on the evaluation of local electron density by controlling the relative electron-deficient (ED) and electron-rich (ER) intensity of monomer at a molecular level based on three rational-designed vinylene-linked sp 2 carbon-covalent organic frameworks (COFs). As expected, the as-prepared vinylene-linked sp 2 carbon-conjugated metal-covalent organic framework (MCOFs) (VL-MCOF-1) with molecular junction exhibited excellent activities for CO 2 -to-HCOOH conversion (283.41 μmol g -1  h -1 ) and high selectivity of 97.1 %, much higher than the VL-MCOF-2 and g-C 34 N 6 -COF, which is due to the synergistic effect of the multi-electronic metal clusters (Cu 3 (PyCA) 3 ) (PyCA=pyrazolate-4-carboxaldehyde) as strong ER roles and cyanopyridine units as ED roles and active sites, as well as the boosted photo-induced charge separation efficiency of vinyl connection and increased light utilization ability. These results not only provide a strategy for regulating the electron-density distribution of photocatalysts at the molecular level but also offers profound insights for metal clusters-based COFs to effective CO 2 conversion., (© 2023 Wiley-VCH GmbH.)

The precise tuning of components, spatial orientations, or connection modes for redox units is vital for gaining deep insight into efficient artificial photosynthetic overall reaction, yet it is still hard achieve for heterojunction photocatalysts. Here, we have developed a series of redox molecular junction covalent organic frameworks (COFs) ( M-TTCOF-Zn, M = Bi, Tri, and Tetra ) for artificial photosynthetic overall reaction. The covalent connection between TAPP-Zn and multidentate TTF endows various connection modes between water photo-oxidation (multidentate TTF) and CO 2 photoreduction (TAPP-Zn) centers that can serve as desired platforms to study the possible interactions between redox centers. Notably, Bi-TTCOF-Zn exhibits a high CO production rate of 11.56 μmol g -1 h -1 (selectivity, ∼100%), which is more than 2 and 6 times higher than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn , respectively. As revealed by theoretical calculations, Bi-TTCOF-Zn facilitates a more uniform distribution of energy-level orbitals, faster charge transfer, and stronger *OH adsorption/stabilization ability than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn .

A series of ferrocene-grafted/loaded stable metal-organic frameworks (MOFs), based on the classical NH 2 -MIL-125(Ti), were prepared to improve the light absorption and photogenerated charge migration of photocatalysts, which can achieve enhanced CO 2 -to-HCOOH reduction performance. This work highlights the obvious advantage of the modifiability of the MOF structure in optimizing the performance of the photocatalytic CO 2 RR.

Artificial photosynthetic diluted CO 2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon-resources recycling utilization. Herein, a three-in-one photocatalytic system of CO 2 enrichment, CO 2 reduction and H 2 O oxidation sites is designed for diluted CO 2 reduction. A Zn-Salen-based covalent organic framework (Zn-S-COF) with oxidation and reductive sites is synthesized; then, ionic liquids (ILs) are loaded into the pores. As a result, [Emim]BF 4 @Zn-S-COF shows a visible-light-driven CO 2 -to-CO conversion rate of 105.88 µmol g -1 h -1 under diluted CO 2 (15%) atmosphere, even superior than most photocatalysts in high concentrations CO 2 . Moreover, natural sunlight driven diluted CO 2 reduction rate also reaches 126.51 µmol g -1 in 5 h. Further experiments and theoretical calculations reveal that the triazine ring in the Zn-S-COF promotes the activity of H 2 O oxidation and CO 2 reduction sites, and the loaded ILs provide an enriched CO 2 atmosphere, realizing the efficient photocatalytic activity in diluted CO 2 reduction., (© 2023 Wiley-VCH GmbH.)

Photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co 14 (L-CH 3 ) 24 , is constructed by directly coordinating metal sites (Co sites) used for the O 2 reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H 2 O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g -1  h -1 for H 2 O 2 production under O 2 -saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host-guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H 2 O 2 synthesis., (© 2023 Wiley-VCH GmbH.)

Electrocatalytic CO 2 reduction (ECR) coupled with organic oxidation is a promising strategy to produce high value-added chemicals and improve energy efficiency. However, achieving the efficient redox coupling reaction is still challenging due to the lack of suitable electrocatalysts. Herein, we designed two bifunctional polyimides-linked covalent organic frameworks (PI-COFs) through assembling phthalocyanine (Pc) and porphyrin (Por) by non-toxic hydrothermal methods in pure water to realize the above catalytic reactions. Due to the high conductivity and well-defined active sites with different chemical environments, NiPc-NiPor COF performs efficient ECR coupled with methanol oxidation reaction (MOR) (Faradaic efficiency of CO (FE CO ) = 98.12%, partial current densities of CO (j CO ) = 6.14 mA cm -2 for ECR, FE HCOOH  = 93.75%, j HCOOH  = 5.81 mA cm -2 for MOR at low cell voltage (2.1 V) and remarkable long-term stability). Furthermore, experimental evidences and density functional theory (DFT) calculations demonstrate that the ECR process mainly conducts on NiPc unit with the assistance of NiPor, meanwhile, the MOR prefers NiPor conjugating with NiPc. The two units of NiPc-NiPor COF collaboratively promote the coupled oxidation-reduction reaction. For the first time, this work achieves the rational design of bifunctional COFs for coupled heterogeneous catalysis, which opens a new area for crystalline material catalysts., (© The Author(s) 2023. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Structural variants of high-nuclearity clusters are extremely important for their modular assembly study and functional expansion, yet the synthesis of such giant structural variants remains a great challenge. Herein, we prepared a lantern-type giant polymolybdate cluster (L-Mo 132 ) containing equal metal nuclearity with the famous Keplerate type Mo 132 (K-Mo 132 ). The skeleton of L-Mo 132 features a rare truncated rhombic triacontrahedron, which is totally different with the truncated icosahedral K-Mo 132 . To the best of our knowledge, this is the first time to observe such structural variants in high-nuclearity cluster built up of more than 100 metal atoms. Scanning transmission electron microscopy reveals that L-Mo 132 has good stability. More importantly, because the pentagonal [Mo 6 O 27 ] n- building blocks in L-Mo 132 are concave instead of convex in the outer face, it contains multiple terminal coordinated water molecules on its outer surface, which make it expose more active metal sites to display superior phenol oxidation performance, which is more higher than that of K-Mo 132 coordinated in M=O bonds on the outer surface., (© 2023 Wiley-VCH GmbH.)

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy) 3 2+ /Fe(bpy) 3 2+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H 2 ) evolution. Rubpy-ZnPor COF achieved the highest H 2 yield (30 338 μmol g -1  h -1 ) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H 2 was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis., (© 2023 Wiley-VCH GmbH.)

H 2 O 2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value-added products. Here, a series of COFs (i.e. Cu 3 -BT-COF, Cu 3 -pT-COF and TFP-BT-COF) with regulated redox molecular junctions have been prepared to study H 2 O 2 photosynthesis coupled with furfuryl alcohol (FFA) photo-oxidation to furoic acid (FA). The FA generation efficiency of Cu 3 -BT-COF was found to be 575 mM g -1 (conversion ≈100 % and selectivity >99 %) and the H 2 O 2 production rate can reach up to 187 000 μM g -1 , which is much higher than Cu 3 -pT-COF, TFP-BT-COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H 2 O 2 production and FFA photo-oxidation to increase the efficiency. This is the first report about COFs for H 2 O 2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous-crystalline catalysts in this field., (© 2023 Wiley-VCH GmbH.)

While the difference in catalytic reactivity between mono- and multimetallic sites is often attributed to more than just the number of active sites, still few catalyst model systems have been developed to explore more underlying causal factors. In this work, we have elaborately designed and constructed three stable calix[4]arene (C4A)-functionalized titanium-oxo compounds, Ti-C4A , Ti 4 -C4A , and Ti 16 -C4A , with well-defined crystal structures, increasing nuclearity, and tunable light absorption capacity and energy levels. Among them, Ti-C4A and Ti 16 -C4A can be taken as model catalysts to compare the differences in reactivity between mono- and multimetallic sites. Taking CO 2 photoreduction as the basic catalytic reaction, both compounds can achieve CO 2 -to-HCOO - conversion with high selectivity (close to 100%). Moreover, the catalytic activity of multimetallic Ti 16 -C4A is up to 2265.5 μmol g -1 h -1 , which is at least 12 times higher than that of monometallic Ti-C4A (180.0 μmol g -1 h -1 ), and is the best-performing crystalline cluster-based photocatalyst known to date. Catalytic characterization combined with density functional theory calculations shows that in addition to the advantage of having more metal active sites (for adsorption and activation of more CO 2 molecules), Ti 16 -C4A can effectively reduce the activation energy required for the CO 2 reduction reaction by completing the multiple electron-proton transfer process rapidly with synergistic metal-ligand catalysis, thus exhibiting superior catalytic performance to that of monometallic Ti-C4A . This work provides a crystalline catalyst model system to explore the potential factors underlying the difference in catalytic reactivity between mono- and multimetallic sites.

The efficient CO 2 electroreduction into high-value products largely relies on the CO 2 adsorption/activation or electron-transfer of electrocatalysts, thus site-specific functionalization methods that enable boosted related interactions of electrocatalysts are much desired. Here, an oriented coordination strategy is reported to introduce N-rich auxiliary (i.e., hexamethylenetetramine, HMTA) into metalloporphyrin metal organic frameworks (MOFs) to synthesize a series of site-specific functionalized electrocatalysts (HMTA@MOF-545-M, M = Fe, Co, and Ni) and they are successfully applied in light-assisted CO 2 electroreduction. Noteworthy, thus-obtained HMTA@MOF-545-Co presents approximately two times enhanced CO 2 adsorption-enthalpy and electrochemical active surface-area with largely decreased impedance-value after modification, resulting in almost twice higher CO 2 electroreduction performance than its unmodified counterpart. Besides, its CO 2 electroreduction performance can be further improved under light-illumination and displays superior FE CO (≈100%), high CO generation rate (≈5.11 mol m -2  h -1 at -1.1 V) and energy efficiency (≈70% at -0.7 V). Theoretical calculations verify that the oriented coordination of HMTA can increase the charge density of active sites, almost doubly enhance the CO 2 adsorption energy, and largely reduce the energy barrier of rate determining step for the boosted performance improvement. This work might promote the development of modifiable porous crystalline electrocatalysts in high-efficiency CO 2 electroreduction., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The selective photoisomerization or photocyclization of stilbene to achieve value upgrade is of great significance in industry applications, yet it remains a challenge to accomplish both of them through a one-pot photocatalysis strategy under mild conditions. Here, a sevenfold interpenetrating 3D covalent organic framework ( TPDT-COF ) has been synthesized through covalent coupling between N , N , N , N -tetrakis(4-aminophenyl)-1,4-benzenediamine (light absorption and free radical generation) and 5,5'-(2,1,3-benzothiadiazole-4,7-diyl)bis[2-thiophenecarboxaldehyde] (catalytic center). The thus-obtained sevenfold interpenetrating structure presents a functional pore channel with a tunable photocatalytic ability and specific pore confinement effect that can be applied for selective stilbene photoisomerization and photocyclization. Noteworthily, it enables photogeneration of cis -stilbene or phenanthrene with >99% selectivity by simply changing the gas atmosphere under mild conditions (Ar, Sele Cis . > 99%, Sele Phen . < 1% and O 2 , Sele Cis . < 1%, and Sele Phen . > 99%). Theoretical calculations prove that different gas atmospheres possess varying influences on the energy barriers of reaction intermediates, and the pore confinement effect plays a synergistically catalytic role, thus inducing different product generation. This study might facilitate the exploration of porous crystalline materials in selective photoisomerization and photocyclization.

Successful establishment of reconnection between retinal ganglion cells and retinorecipient regions in the brain is critical to optic nerve regeneration. However, morphological assessments of retinorecipient regions are limited by the opacity of brain tissue. In this study, we used an innovative tissue cleaning technique combined with retrograde trans-synaptic viral tracing to observe changes in retinorecipient regions connected to retinal ganglion cells in mice after optic nerve injury. Specifically, we performed light-sheet imaging of whole brain tissue after a clearing process. We found that pseudorabies virus 724 (PRV724) mostly infected retinal ganglion cells, and that we could use it to retrogradely trace the retinorecipient regions in whole tissue-cleared brains. Unexpectedly, PRV724-traced neurons were more widely distributed compared with data from previous studies. We found that optic nerve injury could selectively modify projections from retinal ganglion cells in the hypothalamic paraventricular nucleus, intergeniculate leaflet, ventral lateral geniculate nucleus, central amygdala, basolateral amygdala, Edinger-Westphal nucleus, and oculomotor nucleus, but not the superior vestibular nucleus, red nucleus, locus coeruleus, gigantocellular reticular nucleus, or facial nerve nucleus. Our findings demonstrate that the tissue clearing technique, combined with retrograde trans-synaptic viral tracing, can be used to objectively and comprehensively evaluate changes in mouse retinorecipient regions that receive projections from retinal ganglion cells after optic nerve injury. Thus, our approach may be useful for future estimations of optic nerve injury and regeneration., Competing Interests: None

Catalysts capable of electrochemical overall water splitting in acidic, neutral, and alkaline solution are important materials. This work develops bifunctional catalysts with single atom active sites through a pyrolysis-free route. Starting with a conjugated framework containing Fe sites, the addition of Ni atoms is used to weaken the adsorption of electrochemically generated intermediates, thus leading to more optimized energy level sand enhanced catalytic performance. The pyrolysis-free synthesis also ensured the formation of well-defined active sites within the framework structure, providing ideal platforms to understand the catalytic processes. The as-prepared catalyst exhibits efficient catalytic capability for electrochemical water splitting in both acidic and alkaline electrolytes. At a current density of 10 mA cm -2 , the overpotential for hydrogen evolution and oxygen evolution is 23/201 mV and 42/194 mV in 0.5 M H 2 SO 4 and 1 M KOH, respectively. Our work not only develops a route towards efficient catalysts applicable across a wide range of pH values, it also provides a successful showcase of a model catalyst for in-depth mechanistic insight into electrochemical water splitting., (© 2023. The Author(s).)

Rational design of crystalline catalysts with superior light absorption and charge transfer for efficient photoelectrocatalytic (PEC) reaction coupled with energy recovery remains a great challenge. In this work, we elaborately construct three stable titanium-oxo clusters (TOCs, Ti 10 Ac 6 , Ti 10 Fc 8 , and Ti 12 Fc 2 Ac 4 ) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenecarboxylic acid (Fc)) and bifunctionalized ligands (Ac and Fc). They have tunable light-harvesting and charge transfer capacities and thus can serve as outstanding crystalline catalysts to achieve efficient PEC overall reaction, that is, the integration of anodic organic pollutant 4-chlorophenol (4-CP) degradation and cathodic wastewater-to-H 2 conversion. These TOCs can all exhibit very high PEC activity and degradation efficiency of 4-CP. Especially, Ti 12 Fc 2 Ac 4 decorated with bifunctionalized ligands exhibits better PEC degradation efficiency (over 99%) and H 2 generation than Ti 10 Ac 6 and Ti 10 Fc 8 modified with a monofunctionalized ligand. The study of the 4-CP degradation pathway and mechanism revealed that such better PEC performance of Ti 12 Fc 2 Ac 4 is probably due to its stronger interactions with the 4-CP molecule and better • OH radical production. This work not only presents the effective combination of organic pollutant degradation and simultaneously H 2 evolution reaction using crystalline coordination clusters as both anodic and cathodic catalyst but also develops a new PEC application for crystalline coordination compounds.

The inhomogeneous consumption of anions and direct contact between electrolyte and anode during the Zn-deposition process generate Zn-dendrites and side reactions that can aggravate the space-charge effect to hinder the practical implementation of zinc-metal batteries (ZMBs). Herein, electrospray has been applied for the scalable fabrication (>10 000 cm 2 in a batch-experiment) of hetero-metallic cluster covalent-organic-frameworks (MCOF-Ti 6 Cu 3 ) nanosheet-coating (MNC) with integrated micro space electrostatic field for ZMBs anode protection. The MNC@Zn symmetric cell presents ultralow overpotential (≈72.8 mV) over 10 000 cycles at 1 mAh cm -2 with 20 mA cm -2 , which is superior to bare Zn and state-of-the-art porous crystalline materials. Theoretical calculations reveal that MNC with integrated micro space electrostatic field can facilitate the deposition-kinetic and homogenize the electric field of anode to significantly promote the lifespan of ZMBs., (© 2023 Wiley-VCH GmbH.)