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A novel C–N bond activation strategy was established by developing new organic photoredox catalyst (Cz-NI-Ph), which provides a concise approach for the synthesis of amides from tertiary amines.

The metal-polyphenol network has been widely employed in the field of nanodrugs delivery due to its pH-responsiveness.

A metal-free amino-heteroarylation of unactivated olefins via new organic photoredox catalysis was reported, providing a concise and efficient approach for the rapid synthesis of various δ (β, ε)-amino ketones under mild conditions. A series of mechanistic experiments and DFT calculations indicate that this transformation undergoes a photoredox catalytic sequential radical addition/functional group migration process.

Silicic acid modified Ce-W/TiO2 catalyst.

Prostate cancer (PCa) is a common cancer and a major cause of cancer-related death worldwide in men, necessitating novel targets for cancer therapy. High expression of Bloom’s syndrome protein (BLM) helicase is associated with the occurrence and development of PCa. Therefore, the identification and development of new BLM inhibitors may be a new direction for the treatment of PCa. Here, we identified a novel inhibitor by molecular docking and put it to systematic evaluation via various experiments, AO/854, which acted as a competitive inhibitor that blocked the BLM-DNA interaction. Cellular evaluation indicated that AO/854-suppressed tumor growth and metastasis in PC3 cells by enhancing DNA damage, phosphorylating Chk1/Chk2, and altering the p53 signaling pathway. Collectively, the study highlights the potential of BLM as a therapeutic target in PCa and reveals a distinct mechanism by which AO/854 competitively inhibits the function of BLM.

With the recent availability and upgrading of many emerging intestinal microbes sequencing technologies, our research on intestinal microbes is changing rapidly. A variety of investigations have found that intestinal microbes are essential for immune system regulation and energy metabolism homeostasis, which impacts many critical organs. The liver is the first organ to be traversed by the intestinal portal vein, and there is a strong bidirectional link between the liver and intestine. Many intestinal factors, such as intestinal microbes, bacterial composition, and intestinal bacterial metabolites, are deeply involved in liver homeostasis. Intestinal microbial dysbiosis and increased intestinal permeability are associated with the pathogenesis of many chronic liver diseases, such as alcoholic fatty liver disease (AFLD), non-alcoholic fatty liver disease (NAFLD), non-alcoholic steatohepatitis (NASH), chronic hepatitis B (CHB), chronic hepatitis C (CHC), autoimmune liver disease (AIH) and the development of hepatocellular carcinoma (HCC). Intestinal permeability and dysbacteriosis often lead to Lipopolysaccharide (LPS) and metabolites entering in serum. Then, Toll-like receptors activation in the liver induces the exposure of the intestine and liver to many small molecules with pro-inflammatory properties. And all of these eventually result in various liver diseases. In this paper, we have discussed the current evidence on the role of various intestinal microbes in different chronic liver diseases. As well as potential new therapeutic approaches are proposed in this review, such as antibiotics, probiotics, and prebiotics, which may have an improvement in liver diseases.

Aims: Some gene variants in the sodium channels, as well as calcium channels, have been associated with Brugada syndrome (BrS). However, the investigation of the human cellular phenotype and the use of drugs for BrS in presence of variant in the calcium channel subunit is still lacking. Objectives: The objective of this study was to establish a cellular model of BrS in the presence of a CACNB2 variant of uncertain significance (c.425C > T/p.S142F) using human-induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CMs) and test drug effects using this model. Methods and results: This study recruited cells from a patient with Brugada syndrome (BrS) and recurrent ventricular fibrillation carrying a missense variant in CACNB2 as well as from three healthy independent persons. These cells (hiPSC-CMs) generated from skin biopsies of healthy persons and the BrS patient (BrS-hiPSC-CMs) as well as CRISPR/Cas9 corrected cells (isogenic control, site-variant corrected) were used for this study. The hiPSC-CMs from the BrS patient showed a significantly reduced L-type calcium channel current (ICa-L) compared with the healthy control hiPSC-CMs. The inactivation curve was shifted to a more positive potential and the recovery from inactivation was accelerated. The protein expression of CACNB2 of the hiPSC-CMs from the BrS-patient was significantly decreased compared with healthy hiPSC-CMs. Moreover, the correction of the CACNB2 site-variant rescued the changes seen in the hiPSC-CMs of the BrS patient to the normal state. These data indicate that the CACNB2 gene variant led to loss-of-function of L-type calcium channels in hiPSC-CMs from the BrS patient. Strikingly, arrhythmia events were more frequently detected in BrS-hiPSC-CMs. Bisoprolol (beta-blockers) at low concentration and quinidine decreased arrhythmic events. Conclusions: The CACNB2 variant (c.425C > T/p.S142F) causes a loss-of-function of L-type calcium channels and is pathogenic for this type of BrS. Bisoprolol and quinidine may be effective for treating BrS with this variant.

The granule-bound starch synthase I (GBSSI) encoded by the waxy gene is responsible for amylose synthesis in the endosperm of wheat grains. In the present study, a novel Wx-B1 null mutant line, M3-415, was identified from an ethyl methanesulfonate-mutagenized population of Chinese tetraploid wheat landrace Jianyangailanmai (LM47). The gene sequence indicated that the mutated Wx-B1 encoded a complete protein; this protein was incompatible with the protein profile obtained using sodium dodecyl sulfate–polyacrylamide gel electrophoresis, which showed the lack of Wx-B1 protein in the mutant line. The prediction of the protein structure showed an amino acid substitution (G470D) at the edge of the ADPG binding pocket, which might affect the binding of Wx-B1 to starch granules. Site-directed mutagenesis was further performed to artificially change the amino acid at the sequence position 469 from alanine (A) to threonine (T) (A469T) downstream of the mutated site in M3-415. Our results indicated that a single amino acid mutation in Wx-B1 reduces its activity by impairing its starch-binding capacity. The present study is the first to report the novel mechanism underlying Wx-1 deletion in wheat; moreover, it provided new insights into the inactivation of the waxy gene and revealed that fine regulation of wheat amylose content is possible by modifying the GBSSI activity.

Currently, nitrogen fertilizers feed half of the global population, but their use is limited by energy consumption and transportation. Therefore, it is important to study photocatalysts for use in solar nitrogen fertilizers. Herein, a new type of graphene-embedded Ce-based UiO-66 (Ce-UiO-66) photocatalyst (GSCe) is investigated. Ce-UiO-66 is activated by the breakage of benzene-C bonds and the formation of active sites by ultraviolet light in water. Moreover, embedding graphene effectively controls activation and improves nitrogen fixation. GSCe exhibited a remarkable apparent quantum efficiency (AQE) of 9.25 % and stability under 365 nm light with solar-level intensity. GSCe also performed well as a solar ammonia fertilizer for crop cultivation. This investigation opens up opportunities for nitrogen fixation photocatalysts to be used as environmentally friendly solar nitrogen fertilizers.

The controllable synthesis of metal-based nanoclusters for heterogeneous catalytic reactions has received considerable attention. Nevertheless, manufacturing these architectures, while avoiding aggregation and retaining surface activity, remains challenging. Herein, for the first time we designed NiCoFe-Prussian blue analogue (PBA) nanocages as a support for in situ dispersion and anchoring of polymetallic phosphide nanoparticles (pMP-NPs). Benefiting from the porous surfaces and the synergistic effects between pMP-NPs and the cyano groups in PBA, the NiCoFe-P-NP@NiCoFe-PBA nanocages exhibit a significantly enhanced catalytic activity for oxygen evolution reaction (OER) with an overpotential of 223 mV at 10 mA cm-2 and a Tafel slope of 78 mV dec-1, outperforming the NiCoFe-PBA nanocubes, NiCoFe-P nanocages, NiFe-P-NP@NiFe-PBA nanocubes, and CoFe-P-NP@CoFe-PBA nanoboxes. This work not only offers the synthesis strategy of in situ anchoring pMP-NPs on PBA nanocages but also provides a new insight into optimized Gibbs free energy of OER by regulating electron transfer from metallic phosphides to PBA substrate.

Here we describe an unprecedented metal-free C(sp3)-H aroylation of amines via visible-light photoredox catalysis, which provides a straightforward route for the construction of a useful α-amino aryl ketone skeleton. Additionally, a number of selected products exhibit good biological activity for protecting PC12 cell damage, which shows that this skeleton has the potential to become a new neuroprotective agent. Finally, a series of mechanism experiments indicate that this transformation undergoes a photoredox catalytic radical-radical cross-coupling pathway.

The photocatalysis is a very promising technique to address the serious issues of environmental pollution. Among the common photocatalysts, the graphitic carbon nitride (g-C3N4) is widely used for the photodegradation of organic pollutants due to its proper band structure. To further improve the photocatalytic performance of g-C3N4, a novel composite photocatalyst of Co3O4/PT-C3N4 has been prepared by using a one-pot calcination method, in which cobalt tetroxide (Co3O4) nanoparticles as the cocatalyst are introduced on the surface of rectangular hollow g-C3N4 substrate (PT-Co3O4). As a result, the obtained composite photocatalyst (Co3O4/PT-C3N4) delivers an excellent photodegradation performance for diesel oil under a simulated sunlight, which can improve the separation efficiency of the photo-induced electron–hole pairs. The Co3O4/PT-C3N4 composite photocatalyst exhibits a high degradation efficiency of 96.27% after 2 h of visible light, which is much higher than that of the PT-C3N4 photocatalyst. Moreover, the composite photocatalyst can still maintain a high photodegradation efficiency after 10 cycles, exhibiting an excellent cyclic stability. The photo-induced carriers generated by the Co3O4/PT-C3N4 composite photocatalyst follow the Z-scheme heterojunction transfer mechanism. This work gives a fresh idea for the exploration of new high-performance photocatalyst for the treatment of organic environmental pollutants.

The photocatalysis of graphtic carbon nitride (g-C3N4) material has been widely used for the photocatalytic degradation of organic pollutants. However, g-C3N4 still has some drawbacks, such as the high recombination of photo-induced electron–hole pairs and weak absorption of light irradiation. To further improve the photodegradation performance of g-C3N4, a novel composite photocatalyst (CoO/ PT-C3N4) has been prepared by using a one-pot calcination method, in which cobalt oxide (CoO) as a cocatalyst are introduced on the rectangular hollow substrate of g-C3N4 (PT-C3N4), The CoO/PT-C3N4 composite photocatalyst delivers an excellent photodegradation performance for diesel oil under a simulated sunlight. It exhibits a high degradation efficiency of 95.92% after light irradiation for 2 h, which is much higher than that of pristine PT-C3N4. Free radical capture experiments manifest that the free radical of ·O2− plays a major role for the photodegradation and main active radicals abide by the sequence: ·O2− > ·OH > h+. Moreover, the CoO/PT-C3N4 composite photocatalyst delivers an excellent cyclic stability, which only degrades 8.71% photodegradation efficiency after 10 cycles. The improvement of CoO/PT-C3N4 composite photocatalyst is ascribed to the formation of a heterojunction between CoO and PT-C3N4, which promotes the separation of photo-induced carriers. This work paves a new way for the exploration of photocatalyst for the organic pollutant degradation.

Herein, we report a general strategy for the rational design of an efficient organic photocatalyst, and we describe a robust method for the direct C(sp3)–H carbamoylation of saturated aza-heterocyc...

Because organophosphate-based nerve agents still pose a significant threat to society, development of an efficient catalyst for detoxification is highly desirable and yet challenging. In this issue of Chem Catalysis, Farha et al. report a Zr-MOF/hydrogel composite for rapid hydrolysis of nerve agents and achieve the highest efficiency to date under practical conditions.

Solar-driven CO2 conversion into fuels and sustainable energy has attracted increasing attention around the world. However, the efficiency of the transformation remains relatively low due to the rapid recombination of photogenerated charge carriers. In this work, we prepared a ZnIn2S4–ZnAlOx nanocomposite for visible light driven CO2 reduction. The thin layered structure facilitated the photoinduced charge carrier separation and transfer, and also gave excellent adsorption ability towards CO2 molecules. Such a nanocatalyst exhibited excellent activity in visible-light driven CO2 reduction with a CO optimal formation rate of 1100 μmol g−1 h−1, which is 5 times that over bulk ZnIn2S4, and the CO/H2 ratio was increased from 0.2 over bulk ZnIn2S4 to 1.5 over the ZnIn2S4–ZnAlOx composite. In situ FT-IR experiments indicated that CO2 was reduced on ZnIn2S4–ZnAlOx following a COOH* pathway. This work gives insights into the mechanism of the photocatalytic CO2 reduction reaction and inspiration to construct novel heterostructure materials for application in energy and environmental catalysis.

A green and practical divergent Ritter-type amination via a photoredox catalytic four-component radical-polar crossover process was developed. This versatile protocol presents a modular and powerful strategy to access functionalized β-sulfonyl imides and imines under mild conditions from readily available and stable substrates with high atom-, step- and redox economy. We manipulated carboxylic acids and benzotriazoles to precisely attack the nitrilium ion instead of the carbocation, thus preventing many complicated side reactions of the photocatalytic reactions. Furthermore, the synthetic utility of this divergent Ritter reaction is further demonstrated by the late-stage modification of pharmaceutical and natural product derivatives.

The hydrogen evolution reaction (HER) as a fundamental process in electrocatalysis plays a significant role in clean energy technologies. For an energy-efficient HER, it demands an effective, durable, and low-cost catalyst to trigger proton reduction with minimal overpotential and fast kinetics. Here, we successfully fabricate a highly efficient HER catalyst of N-C/Co/Mo2C holey nanorods with Co/β-Mo2C nanoparticles uniformly embedded in nitrogen-doped carbon (N-C/Co/Mo2C) by pyrolyzing the molybdate-coordinated zeolitic imidazolate framework (ZIF-67/MoO42−) holey nanorods, which result from the reaction between CoMoO4 and MeIM in a methanol/water/triethylamine mixed solution. The uniform distribution of MoO42− in the ZIF-67/MoO42− enables Co/β-Mo2C nanoparticles to be well-distributed within nitrogen-doped carbon holey nanorods. This synthetic strategy endows the N-C/Co/Mo2C catalyst with uniformly decorated bimetal, thus attaining excellent HER electrocatalytic activities with a small overpotential of 142.0 mV at 10 mA cm−2 and superior stability in 1.0 mol L−1 KOH aqueous solution.

A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Bronsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.

Homogenization of heterogeneous catalysts by encapsulating metal nanoparticles inside soluble cages is of great interest. Previously organic cages have been used to encapsulate metal nanoparticles, but the limited stabilities and poor water solubilities restrict their applications in conventional catalysis. Here, we report a silica (SiO2)-shelled metal–organic framework (MOF) pyrolysis approach that enables the encapsulation of Ru nanoparticles (RuNPs) into soluble porous carbon cages (SPCCs). By encapsulating RuNPs into nanoscale ZIF-8, covering compact SiO2 layers and performing controllable pyrolysis, RuNPs are well encapsulated inside SPCCs, showing high solubilities and excellent dispersibilities in solvents (water and alcohol), exhibiting excellent O2 and H2 generation rates, with turnover frequencies (TOF) up to 1010 and 1094 min−1 at 303 K, from hydrogen peroxide and from ammonia borane hydrolysis, respectively, representing the top level among the state-of-the-art catalysts. Moreover, owing to the stable structure and the effective confinement of SPCCs, the as-prepared catalysts possess excellent stability and durability.

Through partial deligandation of metal-organic frameworks (MOFs), quasi-MOFs with a transition structure between MOFs and metal compounds (such as metal oxides, nitrides, sulfides, and phosphides) can be fabricated. Quasi-MOFs can not only retain the porous structure of MOFs to a certain extent, but also expose the inorganic nodes to the guest species (e.g., metal nanoparticles) to show enhanced metal-support interaction for synergistic catalysis. This concept was first demonstrated by our group through calcining Au/MIL-101 at different temperatures under Ar flow to adjust the interface between Au nanoparticles and the inorganic Cr-O nodes. The obtained Au/quasi-MIL-101 showed superior enhanced catalytic activity in the oxidation of carbon monoxide. This study has inspired further research interest to fabricate other quasi-MOFs through controlled deligandation of mono- and bimetallic MOFs and their composites for the design of efficient catalysts.

Two-dimensional (2D) metal-organic frameworks (MOFs) are promising for electrocatalysis with high performance, as they possess large surface areas and high densities of exposed active sites. It attracts tremendous attention to obtain 2D nanostructures via simple preparation methods. Herein, a facile pyridine-modulated solvothermal synthesis of Ni/Co bimetallic MOF nanoplates (Ni x Co y -bpy(PyM)) is reported with well-defined 2D morphology with a thickness as thin as 20 nm and an aspect ratio larger than 50. These nanoplates possess oxygen evolution reaction activity as electrocatalysts in alkaline conditions. Specifically, Ni0.5Co1.5-bpy(PyM) exhibits excellent OER electrocatalytic activity with a low overpotential of 256 mV at 10 mA cm−2 and a small Tafel slope of 81.8 mV dec−1 in 1.0 mol L−1 KOH with long-term electrochemical stability for 3000 cyclic voltammetry cycles. The high catalytic activity of Ni0.5Co1.5-bpy(PyM) can be attributed to the in situ formed active hydroxide and oxyhydroxide species within the inherited 2D morphology and the optimized bimetallic ratio.

Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, and high surface area, different types of MOF-based single metal sites are well exploited, including coordinately unsaturated metal sites from metal nodes and metallolinkers, as well as active metal species immobilized to MOFs. Furthermore, controllable thermal transformation of MOFs can upgrade them to nanomaterials functionalized with active single-atom catalysts (SACs). These unique features of MOFs and their derivatives enable them to serve as a highly versatile platform for catalysis, which has actually been becoming a rapidly developing interdisciplinary research area. In this review, we overview the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis. We also compare the results and summarize the major insights gained from the works in this review, providing the challenges and prospects in this emerging field.

Single-atom catalysts have drawn great attention, especially in electrocatalysis. However, most of previous works focus on the enhanced catalytic properties via improving metal loading. Engineering morphologies of catalysts to facilitate mass transport through catalyst layers, thus increasing the utilization of each active site, is regarded as an appealing way for enhanced performance. Herein, we design an overhang-eave structure decorated with isolated single-atom iron sites via a silica-mediated MOF-templated approach for oxygen reduction reaction (ORR) catalysis. This catalyst demonstrates superior ORR performance in both alkaline and acidic electrolytes, comparable to the state-of-the-art Pt/C catalyst and superior to most precious-metal-free catalysts reported to date. This activity originates from its edge-rich structure, having more three-phase boundaries with enhanced mass transport of reactants to accessible single-atom iron sites (increasing the utilization of active sites), which verifies the practicability of such a synthetic approach.

Porous metal phosphide cubes with exposed vertices and edges containing abundant catalytically active sites are promising electrocatalysts. Herein, by integrating the advantages of the phosphorus-rich cobalt phosphides and bimetallic oxides to form hybrid architectures, we prepared CoP3/CoSnO2 via phosphating CoSn(OH)6 nanocubes, which has unique porous nanocubic structure. The optimized CoP3/CoSnO2 porous nanaocubes showed excellent electrocatalytic activity for OER/ORR. What’s more, the electrochemical performances of CoP3/CoSnO2 porous nanaocubes as air cathode catalyst for zinc air batteries were better than that of commercial RuO2 and 20 wt% Pt/C with a mass ratio of 1:1 as the air cathode catalyst. This work offers a new strategy to fabricate metal phosphide with porous nanocubic structures.

Two dimensional (2D) ultrathin nonprecious metal based catalysts show excellent electrocatalytic activities, due to the larger surface areas, more catalytic sites and more interconnected electron-transfer access than their bulk counterparts. Here, we synthesized cobalt pyrophosphate (Co2P2O7) nanosheets with different thickness by a simple and efficient one-step hydrothermal process. The catalytic performance of the obtained Co2P2O7 was investigated via diverse electrochemical measurement. Due to the unique 2D structure and the flexible coordination of pyrophosphate group, the as-prepared Co2P2O7 catalyst had excellent electrocatalytic performance and good stability, which could rank among the most active nonprecious metal catalysts for oxygen evolution reaction and oxygen reduction reaction. In addition, the ultrathin Co2P2O7 nanosheets exhibited good performance as the air cathode catalyst for zinc air batteries.

Fabricating a low-cost and highly efficient electrocatalyst is of importance for the development of renewable energy devices. In this work, we have synthesized an ultrafine cobalt oxide nanocatalyst (5-10 nm) doped with boron (BC/Co3 O4 ) by using a metal-organic framework as a precursor, which exhibits an excellent catalytic activity for oxygen evolution reaction (OER). Owing to the improvement of accessible active sites by boron doping, the synthesized catalyst can reach a current density of 10 mA cm-2 at 1.54 V with a low overpotential of 310 mV, superior than those of commercial RuO2 and N-doped C/Co3 O4 . This work provides a facile way to develop highly efficient catalysts for electrochemical reactions.

Attractive materials fundamentally depend on both performance and industrialization potential. To address the scale-up concern, a simple and highly effective synthesis of porous organic polymers from commercial building blocks/monomers is urgently needed. Here we report the fabrication of amino-functionalized hypercrosslinked polymer nanoparticles (AHCPNPs) for CO2 capture by utilizing commercial polystyrene (PS) as the main building blocks and poly(tert-butyl acrylate)-b-poly(styrene) (PtBA-b-PS) diblock copolymers as a stabilizer. The 2-step synthetic strategy includes hypercrosslinking of benzene units in PS and PtBA-b-PS chains and subsequent aminolysis reaction of the acrylate-unit in PtBA-b-PS chains by diamine compounds. The AHCPNPs demonstrate a well-defined microporous structure with a specific surface area of up to 507.64 m2 g−1 and an extreme capacity of 53.65 w% (12.21 mmol g−1) for carbon dioxide adsorption. The definite control over the particle size and porous properties of these AHCPNPs has been achieved by changing the BA/S ratio of the diblock copolymers and the mass ratio of PtBA-b-PS to PS. Our findings may open up a new avenue for scale-up fabrication that possesses a well-porous structure from commercial polymeric materials and thus generate valuable breakthroughs in many applications, especially in industrialization.

The present study investigated the fabrication of hollow spheres of a silica–ruthenium–nickel composite catalyst for the hydrolytic dehydrogenation of ammonia borane. The hollow spheres were obtained via the originally developed in situ synthesis method. In this method, the hollow spheres were formed by treating in an aqueous solution, including sodium borohydride and ammonia borane, from spherical silica–nickel–ruthenium composite particles prepared via a sol–gel method. In this process, the formation of hollow voids, the activation of active ruthenium and nickel species and the hydrolysis of ammonia borane for hydrogen evolution occurred parallely. Compared to the catalytic activity of hollow spheres with various ruthenium/(ruthenium + nickel) ratios and to the total amount of metals, the hollow spheres with a ruthenium/(ruthenium + nickel) ratio = 0.5 and a total amount of metals = 8.0 mol% showed the highest activity for the hydrogen evolution with a comparative turnover frequency (33.6 mol-H2 min−1 [mol-(Ru + Ni)]−1) of the previously reported catalyst. The hollow spheres included spherical particles with a diameter of the hollow void = ca. 250 nm, and their specific surface area was about ten times as high as the spherical particle precursor, indicating that the obtained hollow spheres consisted of a porous structure. The highly active hollow spheres showed cycle ability for hydrogen evolution and their activity did not significantly decrease with the increase in the cycle number.

Hybrid catalysis provides an effective pathway to improve the catalytic efficiency and simplify the synthesis operation, but multiple catalytic sites are required. Catalysts with multiple functions based on/derived from metal-organic frameworks (MOFs) have received growing attention in organic synthesis due to their wide variety and outstanding designability. This review provides an overview of significant advances in the field of organic reactions by MOF-based hybrid catalysts with emphasis on multiple catalytic sites and their synergies, including inherent sites on host frameworks, sites of MOF composites and metal sites in/on MOF-derived hybrid catalysts.

Single/dual-atom and cluster metal catalysts, with much higher atom-utilization efficiency, remarkable performance, good recyclability and unique properties, have emerged as a new frontier in energy-related catalysis. In recent years, metal–organic frameworks (MOFs) have demonstrated great potential for the targeted creation of single/dual-atom and cluster catalysts, featuring the distinctive advantages of high metal loadings, porous structures and tailorable catalytic sites. In this review, we discuss the key roles and the critical issues of single/dual-atom and cluster catalysts, and the great opportunities furnished by MOFs for the construction strategy. The accessible characterization techniques for single/dual-atom and cluster catalysts will be showcased. Furthermore, we highlight recent advances in the construction and energy applications of MOF-based single/dual-atom and cluster catalysts by taking advantage of structural features of MOFs. Current issues, promising ideas and future prospects for MOF-based single/dual-atom and cluster catalysts are given.

An efficient and green method was proposed to synthesise Au nanoparticle (Au NP)-decorated Fe3O4@porous carbon core–shell nanoparticles (denoted as Fe3O4@C–Au). In this synthetic strategy, polydopamine (PDA) was prepared by spontaneous polymerization of dopamine, which works as both a carbon precursor and a reducing agent. The thickness of the carbon layer is about 50 nm and could be easily adjusted by changing the polymerization time. The as-prepared Fe3O4@C–Au, which was well characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS) and Fourier transform infrared (FTIR), showed excellent catalytic performance in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in aqueous solution using sodium borohydride as a hydrogen source. Owing to its superparamagnetic property of the Fe3O4 core and the stability of the carbon shell, the catalyst could be easily separated using an external magnet and shows excellent reusability (almost the same activity as the fresh catalyst after eight catalytic cycles). The facile and green preparation, high catalytic capability and recyclability give Fe3O4@C–Au a great development potential in the industrial wastewater treatment.

Bimetallic metal–organic frameworks (MOFs) have two different metal ions in the inorganic nodes. According to the metal distribution, the architecture of bimetallic MOFs can be classified into two main categories namely solid solution and core–shell structures. Various strategies have been developed to prepare bimetallic MOFs with controlled compositions and structures. Bimetallic MOFs show a synergistic effect and enhanced properties compared to their monometallic counterparts and have found many applications in the fields of gas adsorption, catalysis, energy storage and conversion, and luminescence sensing. Moreover, bimetallic MOFs can serve as excellent precursors/templates for the synthesis of functional nanomaterials with controlled sizes, compositions, and structures. Bimetallic MOF derivatives show exposed active sites, good stability and conductivity, enabling them to extend their applications to the catalysis of more challenging reactions and electrochemical energy storage and conversion. This review provides an overview of the significant advances in the development of bimetallic MOFs and their derivatives with special emphases on their preparation and applications., This review summarizes the design and synthesis of bimetallic MOFs and their derivatives, with superior performance to their monometallic counterparts in many applications.

Striking effects are expected in solid-solution alloying, which offers enormous possibilities for various applications, especially in industrial catalysis. However, phase diagrams have revealed that a wide range of metallic elements are immiscible with each other even above their melting points. Achieving such unknown alloying between different immiscible metallic elements is highly desirable but challenging. Here, for the first time, by using an innovative solid ligand-assisted approach, we achieve the solid-solution alloying between the bulk-immiscible Au and Rh in plenty of clean, ultrafine (∼ 1.6 nm) and highly dispersed nanoclusters. The solid-solution alloying of immiscible Au and Rh significantly enhances their catalytic performance toward the hydrogen evolution from formic acid in contrast to the monometallic Au and Rh nanoclusters. Moreover, the resultant binary solid-solution nanoclusters are stable without any segregation during catalytic reactions. The approach demonstrated here for homogeneously mixing the immiscible metals at the atomic scale will benefit the creation of advanced alloys and their catalytic applications in future.

The development of chiral architectures for chiral ligand and catalyst discovery is essential for asymmetric catalysis. Herein, we report the concise synthesis of a Si-centered spirocyclic skeleton, spirobiphenoxasilin-diol (SPOSiOL), and its derived chiral ligands. Using the chemical resolution method, the optical SPOSiOL could be obtained in high yield on a gram scale. Preliminary studies indicated that this ligand scaffold has great potential in transition metal-catalyzed asymmetric reactions. This finding further highlights that the Si-centered spirocyclic scaffolds are of great value in asymmetric catalysis.

Over the past years, impressive progress has been made in the development of organic photoredox catalytic cascade reactions without the participation of expensive and toxic transition metals under visible light irradiation. These transformations highly depend on the in situ generation of various radical species in the photoredox catalytic cycles. Numerous chemically and biomedically valuable building blocks have been synthesized through this efficient and sustainable protocol. In this review, we highlight the recent progress in this blooming area by presenting a series of new catalytic cascade reactions mediated by organic photoredox catalysts and describe their mechanisms and applications which have appeared in the recent literature.

Hierarchical micro-/mesoporous carbons with abundant Fe-N-C sites were prepared through one-step carbonization of a metal-organic framework (MOF) with sodium iron ethylenediaminetetraacetic acid [NaFe(III)EDTA], which can facilitate the nucleation and growth of ultrafine (∼1.4 nm) and highly dispersed palladium nanoparticles (Pd NPs). Interfacing Pd NPs with Fe-N-C sites has been demonstrated for the first time to boost the heterogeneous catalysis of hydrogen production from formic acid, affording an ultrahigh turnover frequency (TOF) value of 7361 h-1 at 323 K. The robust synergistic interactions between Pd NPs and Fe-N-C sites together with the small size effects of Pd NPs are responsible for the enhanced catalytic activity.

The largest source of resistant bacteria or viruses is the overuse and misuse of antibiotics in humans and animals. These resistant bacteria or viruses may evolve into superbacteria or superviruses, which causes global plague. Therefore, it is significant to find a highly efficiency and low-cost method to eliminate antibiotics in water environment from inappropriate discharge. Here, a highly active and highly stable heterogeneous catalyst, Cu0.76Co2.24O4/SBA-15 (CCS) was prepared for peroxymonosulfate (PMS) activation in aim of decomposing persistent sulfapyridine (SPD). The reaction mechanism was thoroughly investigated via in situ quenching test and in situ electron paramagnetic resonance. Four reactive species, SO4·-, O2·-, 1O2 and ·OH were generated in Cu0.76Co2.24O4/SBA-15/PMS (CCSP) system. The SO4·- and O2·- were dominant active species responsible for SPD degradation. Co(Ⅱ)↔Co(Ⅲ)↔Co(Ⅱ) redox reaction cycle was constructed due to the different redox potential of Co(Ⅱ)/Co(Ⅲ), HSO5-/SO4∙-, and HSO5-/SO5∙-. Interestingly, Cu(Ⅰ) could urge the redox reaction cycle for PMS activation to be more thermodynamically feasible. Therefore, CCS possessed a highly catalytic activity and excellent stability. Meanwhile, the anions interference test indicated Cl-, NO3-, HCO3-, and H2PO4- had almost no inhibitory effect on SPD degradation over this catalytic system. We sincerely expected that this catalyst system would be applied extensively into antibiotics degradation in real water bodies.

Carbon nanospheres (XC-72R) were functionalized by boron-oxygen (B-O) through coannealing with boric acid, to which highly dispersed palladium nanoparticles (Pd NPs) (~ 1.7 nm) were immobilized by a wet chemical reduction for the first time. The resultant Pd/OB-C catalyst exhibits significantly improved activity for the dehydrogenation from formic acid (FA) compared to pristine XC-72R supported Pd NPs (Pd/C). Impressively, by adding melamine precursor, the B-O and nitrogen (N)-functionalized product OB-C-N displays an extremely high B content, ca. 34 times higher than OB-C. The Pd/OB-C-N catalyst with an ultrafine Pd particle size of ~ 1.4 nm shows a superb activity, with a turnover frequency (TOF) as high as 5,354 h−1 at 323 K, owing to the uniform ultrafine Pd NPs and the effect from B-O and N functionalities.

A method using aroyl chlorides as atom-transfer radical cyclization agents in a novel visible-light photocatalytic aroylchlorination reaction is developed. The overall transformation involves the formation of two new C-C bonds and one new C-Cl bond in a one-pot process. The advantages of this reaction include high atom/step/redox economy, mild conditions, operational simplicity, and broad substrate scopes.

A combined acid–alkali hydrothermal method was used to prepare fly ash –derived SAPO-34 molecular sieves from a thermal power plant in Inner Mongolia (China). The specific surface area of the prepared fly-ash-derived SAPO-34 molecular sieves was 579 m2 g−1, the total pore volume was about 0.27 cm3 g−1, and the pore size was 0.56 nm; the molar ratios of Al2O3:P2O5:SiO2 were 1:0.86:0.45. Cu/SAPO-34 catalysts were prepared by impregnation of low-cost fly-ash-derived SAPO-34 molecular sieves as a support and tested in selective catalytic reduction with NH3 (NH3-SCR). Powder X-ray diffraction (XRD), N2 adsorption–desorption, X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), NH3 temperature-programmed desorption (NH3-TPD), electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), X-ray fluorescence analysis (XRF) and scanning electron microscopy (SEM) were used for catalyst characterization and investigation of the relationships between the catalyst structure and the catalytic activity. The actual silica:alumina ratio of the molecular sieves did not increase with increasing Cu loading, indicating that increasing the Cu loading does not change the original structure of the SAPO-34 molecular sieves. The XRF and NMR results showed that replacement by Cu results in more Si islands. The molecular sieve acidity decreased because of the increased number of Si islands. The NH3-TPD results showed that for the Cu/SAPO-34 catalysts there was a low correlation between the low-temperature activity and the amount of acidic sites. SCR activity is closely related to the location of Cu. The 4.47Cu/SAPO-34 catalyst has the highest isolated Cu2+ showed the highest NH3-SCR activities (> 90%) at 250–350 °C. This work opens up new avenues for recycling fly ash formed in coal-fired power plants (reducing environmental pollution) and developing low-cost SCR catalysts for NOx pollution control. Keywords: Fly-ash-derived SAPO-34, Low-temperature NH3-SCR, Cu/SAPO-34, Cu content, Cu species

Metal-organic frameworks (MOFs) have emerged as a promising class of materials with several unique properties, such as high porosity, diverse composition, tunable pore structures, and versatile functionality. These characteristics enable MOFs to show potential in the field of heterogeneous catalysis. To satisfy the practical applications of MOFs, controllable integration of MOFs and functional materials (e.g., metal nanoparticles, quantum dots, polyoxometalates, molecular species, enzymes, silica, and polymers) can enhance the characteristics of MOFs through activity improvement and framework stabilization. In MOF composites/hybrids, functional materials can cooperatively work with MOFs to show enhanced catalytic activity, selectivity, and stability in a variety of chemical transformations. This review provides an overview of the significant advances in the development of diverse MOF composites/hybrids with special emphases on the preparation and catalytic applications.

We demonstrate the preparation and electrochemical behavior of Pt/IrO2Nb2O5–rGO composite for oxygen reduction reaction, in which IrO2Nb2O5–rGO is firstly synthesized by one-pot hydrothermal process, and Pt is then supported on it through microwave-assisted polyol process. It is found that Nano-scaled Pt/IrO2Nb2O5 hybrid particles (ca. 6.3 nm) are well dispersed throughout the rGO sheets. Doping Ir into Nb2O5 and incorporation of rGO helps improve the catalytic performance. The kinetic current density of Pt/IrO2Nb2O5–rGO is 8.4 times higher than Pt/Nb2O5 catalyst. The special Pt/IrO2Nb2O5–rGO structure with interactions helps enhance the stability of Pt NPs. An improved Pt/IrO2Nb2O5–rGO electrocatalyst is synthesized, and it shows that doping Ir into Nb2O5 and incorporation of rGO helps improve the catalytic performance.

The catalytic performance of Hg0 oxidation over vanadium-based SCR catalysts modified by different addition amounts of CuO was investigated. All catalysts were prepared by impregnation method and characterized. The 7% Cu/VWTi exhibited high Hg0 oxidation as well as a desired NO removal efficiency at 280–360 °C. The characterization revealed the enhancement of redox properties and well-dispersed active species results in the high catalytic performance after modification. The incorporation model showed that CuO in 7% Cu/VWTi was present in the monolayer dispersion, leading to the highest performance. Moreover, the effects of O2, NO, SO2, NH3 and HCl were explored. It showed all flue gas except NH3 could promote Hg0 oxidation. Fortunately, the inhibiting effect of NH3 could be scavenged if the catalyst is installed at the downstream of the SCR reactor. In addition, the mechanism of Hg0 oxidation over Cu/VWTi was discussed.

Highly active bimetallic PdAu nanoparticles (NPs) supported on commercial nanocarbons have been prepared through a simple L-arginine-mediated synthetic approach. The as-synthesized catalysts have been used for the dehydrogenation of formic acid (FA). Remarkably, the resultant Pd1Au1 NPs immobilized onto MSC-30 carbon achieved a turnover frequency (TOF) value of 8355 h−1 at 60 °C in aqueous FA solution without addition of sodium formate, much higher than the results of heterogeneous catalysts reported thus far. The simple small-molecule-mediated synthetic methodology developed herein opens a new path for the practical and large-scale development of high-performance catalysts for a wide range of applications.