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Systematic construction of isoreticular hydrogen-bonded organic frameworks (HOFs) promises tailored material properties crucial for diverse applications, yet is challenging due to the weak, flexible, and non-directional nature of hydrogen bonds. Herein, we develop an "integrated monomer synthesis-framework assembly" (ISA) methodology for constructing a series of isoreticular HOFs. Unlike traditional methods where monomers are first synthesized and then assembled into HOFs, the ISA system employs dicyandiamide rigid hydrogen-bonded hexameric clusters as connecting nodes to covalently react with planarized C 3 -symmetric cyano-precursors (C 3 -CPs) to generate diaminotriazine (DAT) monomers, while simultaneously inducing the directional assembly into isoreticular (6,3)-net hcb topological DAT-C 6 -HOFs. The pore sizes and microenvironments of the resulting DAT-C 6 -HOFs can be precisely tuned by varying the structural modulation (length and steric hindrance) of the π-bridge on C 3 -CPs, enabling highly selective sensing towards perfluorooctanoic acid over other homologous molecules, that are difficult to be separated and detected by chromatography. Overall, the ISA methodology facilitates the scalable creation of families of isostructural HOFs and provides a customized structural platform for investigating factors beyond topology that impact the capturing, releasing, and responding to guest molecules., (© 2024 Wiley-VCH GmbH.)

Transition metal sulfides, particularly heterostructures, represent a promising class of electrocatalysts for two electron oxygen reduction (2e - ORR), however, understanding the dynamic structural evolution of these catalysts during alkaline ORR remains relatively unexplored. Herein, NiS 2 /In 2.77 S 4 heterostructure was synthesized as a precatalyst and through a series of comprehensive ex situ and in situ characterizations, including X-ray absorption spectroscopy, Raman spectroscopy, transient photo-induced voltage measurements, electron energy loss spectroscopy, and spherical aberration-corrected electron microscopy, it was revealed that nickel/indium (oxy)hydroxides (NiOOH/In(OH) 3 ) could be evolved from the initial NiS 2 /In 2.77 S 4 via both electrochemical and chemical-driven methods. The electrochemical-driven phase featured abundant bridging oxygen-deficient [NiO 6 ]-[InO 6 ] units at the interfaces of NiOOH/In(OH) 3 , facilitating a synergistic effect between active Ni and In sites, thus enabling an enhanced alkaline 2e - ORR capability than that of chemical-driven process. Remarkably, electrochemically induced NiOOH/In(OH) 3 exhibited exceptional performance, achieving H 2 O 2 selectivity of >90 % across the wide potential window (up to 0.4 V) with a peak selectivity of >99 %. Notably, within the three-electrode flow cell, a current density of 200 mA cm -2 was sustained over 20 h, together with an impressive Faradaic efficiency of ~90 % during the whole cycle process., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We introduce a "solution-processing-transformation" strategy, deploying solvent vapor as scaffolds, to fabricate high-quality hydrogen-bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor-trigged in situ transformation of dense amorphous supramolecules to crystalline HOF-16, with HOF-11 as the transient state. The mechanism involves a vapor-activated dissolution-precipitation equilibrium shifting and hydrogen bonding-guided molecule rearrangement, elucidated through combined experimental and theoretical analysis. Upon removal of the molecular scaffolds, the resulting HOF-16 membranes showcase significant improvement in hydrogen separation performance over their amorphous counterparts and previously reported HOF membranes. The method's broad applicability is evidenced by successfully extending it to other substrates and HOF structures. This study provides a fundamental understanding of guest-induced ordered supramolecular assembly and paves the way for the advanced manufacture of high-performance HOF membranes for gas separation processes., (© 2024 Wiley-VCH GmbH.)

2D-3D tin-based perovskites are considered as promising candidates for achieving efficient lead-free perovskite solar cells (PSCs). However, the existence of multiple low-dimensional phases formed during the film preparation hinders the efficient transport of charge carriers. In addition, the non-homogeneous distribution of low-dimensional phases leads to lattice distortion and increases the defect density, which are undesirable for the stability of tin-based PSCs. Here, mixed spacer cations [diethylamine (DEA + ) and phenethylamine (PEA + )] are introduced into tin perovskite films to modulate the distribution of the 2D phases. It is found that compared to the film with only PEA + , the combination of DEA + and PEA + favors the formation of homogeneous low-dimensional perovskite phases with three octahedral monolayers (n = 3), especially near the bottom interface between perovskite and hole transport layer. The homogenization of 2D phases help improve the film quality with reduced lattice distortion and released strain. With these merits, the tin PSC shows significantly improved stability with 94% of its initial efficiency retained after storing in a nitrogen atmosphere for over 4600 h, and over 80% efficiency maintained after continuous illumination for 400 h., (© 2024 Wiley‐VCH GmbH.)

Supercontinuum generation (SCG) from silica-based photonic crystal fibers (PCFs) is of highly technological significance from microscopy to metrology, but has been hindered by silica's relatively low intrinsic optical nonlinearity. The prevailing approaches of filling PCF with nonlinear gases or liquids can endow fibre with enhanced optical nonlinearity and boosted SCG efficiency, yet these hybrids are easily plagued by fusion complexity, environmental incompatibility or transmission mode instability. Here this work presents a strategy of embedding solid-state 2D MoS 2 atomic layers into the air-holes of PCF to efficiently enhance SCG. This work demonstrates a 4.8 times enhancement of the nonlinear coefficient and a 70% reduction of the threshold power for SCG with one octave spanning in the MoS 2 -PCF hybrid. Furthermore, this work finds that the SCG enhancement is highly layer-dependent, which only manifests for a real 2D regime within the thickness of five atomic layers. Theoretical calculations reveal that the critical thickness arises from the trade-off among the layer-dependent enhancement of the nonlinear coefficient, leakage of fundamental mode and redshift of zero-dispersion wavelength. This work provides significant advances toward efficient SCG, and highlights the importance of matching an appropriate atomic layer number in the design of functional 2D material optical fibers., (© 2024 Wiley‐VCH GmbH.)

Dual-single-atom catalysts (DSACs) are the next paradigm shift in single-atom catalysts because of the enhanced performance brought about by the synergistic effects between adjacent bimetallic pairs. However, there are few methods for synthesizing DSACs with precise bimetallic structures. Herein, a pre-coordination strategy is proposed to precisely synthesize a library of DSACs. This strategy ensures the selective and effective coordination of two metals via phthalocyanines with specific coordination sites, such as -F- and -OH-. Subsequently, in situ confinement inhibits the migration of metal pairs during high-temperature pyrolysis, and obtains the DSACs with precisely constructed metal pairs. Despite changing synthetic parameters, including transition metal centers, metal pairs, and spatial geometry, the products exhibit similar atomic metal pairs dispersion properties, demonstrating the universality of the strategy. The pre-coordination strategy synthesized DSACs shows significant CO 2 reduction reaction performance in both flow-cell and practical rechargeable Zn-CO 2 batteries. This work not only provides new insights into the precise synthesis of DSACs, but also offers guidelines for the accelerated discovery of efficient catalysts., (© 2024 Wiley-VCH GmbH.)

Electrocatalytic carbon dioxide reduction into high-value chemicals is one of the important solutions to the greenhouse effect and energy crisis. However, the slow kinetic process of eight electrons requires the development of efficient catalysts to improve the yields. Single atom catalysts (SACs) with high activity and selectivity have become an emerging research frontier in the field of heterogeneous catalysis. Herein, a catalyst comprised of Cu single atoms loaded on carbon substrate (Cu-NC) is developed for highly selective electrocatalytic reduction of CO 2 to methane (CH 4 ). The optimal catalyst (Cu-NC-1-4) exhibits a faradaic efficiency (FE) of over 50 % for CH 4 within a wide potential window from -1.3 V to -1.8 V (vs. RHE) and the highest FE of CH 4 is up to 67.22 % at -1.6 V (vs. RHE). Meanwhile, the product selectivity of CH 4 among all the carbon products reaches 93.00 %, and the activity decay can be negligible via the 70-hour-stability-test. The existence of atomic dispersed Cu-N 3 sites was verified by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption near edge structure (XANES). Density functional theory (DFT) calculations show that the effective adsorption of the key intermediate *CO on Cu-N 3 sites prompts the generation of CH 4 ., (© 2024 Wiley-VCH GmbH.)

All-inorganic cesium lead triiodide perovskites (CsPbI 3 ) have attracted increasing attention due to their good thermal stability, remarkable optoelectronic properties, and adaptability in tandem solar cells. However, N 2 -filled glovebox is generally required to strictly control the humidity during film fabrication due to the moisture-induced black-to-yellow phase transition, which remains a great hinderance for further commercialization. Herein, we report an effective approach via incorporating multifunctional ethacridine lactate (EAL) to mitigate moisture invasion and enable the fabrication of efficient inverted (p-i-n) CsPbI 3 perovskite solar cells (PSCs) under ambient condition. It is revealed that the lactate anions accelerate the crystallization of CsPbI 3 , shortening the exposure time to moisture during film fabrication. Meanwhile, the conjugated backbone and multiple functional groups in the ethacridine cations can interact with I - and Pb 2+ to reduce the undesired defects, stabilize the perovskite structure and facilitate the charge transport in the film. Moreover, EAL incorporation also leads to better energy alignment, thus favoring charge extraction at both upper and bottom interfaces. Consequently, the device efficiency and stability are enormously enhanced, with the champion efficiency reaching 21.08 %. This even surpasses the highest value reported for the devices fabricated in glovebox, representing a record efficiency of inverted all-inorganic PSCs., (© 2024 Wiley-VCH GmbH.)

Zinc dendrite, active iodine dissolution, and polyiodide shuttle caused by the strong interaction between liquid electrolyte and solid electrode are the chief culprits for the capacity attenuation of aqueous zinc-iodine batteries (ZIBs). Herein, mullite is adopted as raw material to prepare Zn-based solid-state electrolyte (Zn-ML) for ZIBs through zinc ion exchange strategy. Owing to the merits of low electronic conductivity, low zinc diffusion energy barrier, and strong polyiodide adsorption capability, Zn-ML electrolyte can effectively isolate the redox reactions of zinc anode and AC@I 2 cathode, guide the reversible zinc deposition behavior, and inhibit the active iodine dissolution as well as polyiodide shuttle during cycling process. As expected, wide operating voltage window of 2.7 V (vs Zn 2+ /Zn), high Zn 2+ transference number of 0.51, and low activation energy barrier of 29.7 kJ mol -1 can be achieved for the solid-state Zn//Zn cells. Meanwhile, high reversible capacity of 127.4 and 107.6 mAh g -1 can be maintained at 0.5 and 1 A g -1 after 3 000 and 2 100 cycles for the solid-state Zn//AC@I 2 batteries, corresponding to high-capacity retention ratio of 85.2% and 80.7%, respectively. This study will inspire the development of mineral-derived solid electrolyte, and facilitate its application in Zn-based secondary batteries., (© 2024 Wiley‐VCH GmbH.)

l-2-Hydroxyglutarate (l-2-HG) is a functionally compartmentalized metabolite involved in various physiological processes. However, its subcellular distribution and mitochondrial transport remain unclear owing to technical limitations. In the present study, an ultrasensitive l-2-HG biosensor, sfLHGFR H , composed of circularly permuted yellow fluorescent protein and l-2-HG-specific transcriptional regulator, is developed. The ability of sfLHGFR H to be used for analyzing l-2-HG metabolism is first determined in human embryonic kidney cells (HEK293FT) and macrophages. Then, the subcellular distribution of l-2-HG in HEK293FT cells and the lower abundance of mitochondrial l-2-HG are identified by the sfLHGFR H -supported spatiotemporal l-2-HG monitoring. Finally, the role of the l-glutamate transporter SLC1A1 in mitochondrial l-2-HG uptake is elucidated using sfLHGFR H . Based on the design of sfLHGFR H , another highly sensitive biosensor with a low limit of detection, sfLHGFR L , is developed for the point-of-care diagnosis of l-2-HG-related diseases. The accumulation of l-2-HG in the urine of patients with kidney cancer is determined using the sfLHGFR L biosensor., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Designing solid electrolyte is deemed as an effective approach to suppress the side reaction of zinc anode and active material dissolution of cathodes in liquid electrolytes for zinc metal batteries (ZMBs). Herein, kaolin is comprehensively investigated as raw material to prepare solid electrolyte (KL-Zn) for ZMBs. As demonstrated, KL-Zn electrolyte is an excellent electronic insulator and zinc ionic conductor, which presents wide voltage window of 2.73 V, high ionic conductivity of 5.08 mS cm -1 , and high Zn 2+ transference number of 0.79. For the Zn//Zn cells, superior cyclic stability lasting for 2200 h can be achieved at 0.2 mA cm -2 . For the Zn//NH 4 V 4 O 10 batteries, stable capacity of 245.8 mAh g -1 can be maintained at 0.2 A g -1 after 200 cycles along with high retention ratio of 81 %, manifesting KL-Zn electrolyte contributes to stabilize the crystal structure of NH 4 V 4 O 10 cathode. These satisfying performances can be attributed to the enlarged interlayer spacing, zinc (de)solvation-free mechanism and fast diffusion kinetics of KL-Zn electrolyte, availably guaranteeing uniform zinc deposition for zinc anode and reversible zinc (de)intercalation for NH 4 V 4 O 10 cathode. Additionally, this work also verifies the application possibility of KL-Zn electrolyte for Zn//MnO 2 batteries and Zn//I 2 batteries, suggesting the universality of mineral-based solid electrolyte., (© 2024 Wiley-VCH GmbH.)

The rational design of MoS 2 /carbon composites have been widely used to improve the lithium storage capability. However, their deep applications remain a big challenge due to the slow electrochemical reaction kinetics of MoS 2 and weak bonding between MoS 2 and carbon substrates. In this work, anthracite-derived porous carbon (APC) is sequential coated by TiO 2 nanoparticles and MoS 2 nanosheets via a chemical activation and two-step hydrothermal method, forming the unique APC@TiO 2 @MoS 2 ternary composite. The dynamic analysis, in-situ electrochemical impedance spectroscopy as well as theoretical calculation together demonstrate that this innovative design effectively improves the ion/electron transport behavior and alleviates the large volume expansion during cycles. Furthermore, the introduction of middle TiO 2 layer in the composite significantly strengthens the mechanical stability of the entire electrode. As expected, the as-prepared APC@TiO 2 @MoS 2 anode displays a high lithium storage capacity with a reversible capacity of 655.8 mAh g -1 after 150 cycles at 200 mA g -1 , and robust cycle stability. Impressively, even at a high current density of 2 A g -1 , the electrode maintains a superior reversible capacity of 597.7 mAh g -1 after 1100 cycles. This design highlights a feasibility for the development of low-cost anthracite-derived porous carbon-based electrodes., (© 2024 Wiley-VCH GmbH.)

The instability of the solid electrolyte interface (SEI) is a critical challenge for the zinc metal anodes, leading to an erratic electrode/electrolyte interface and hydrogen evolution reaction (HER), ultimately resulting in anode failure. This study uncovers that the fluorine species dissolution is the root cause of SEI instability. To effectively suppress the F - dissolution, an introduction of a low-polarity molecule, 1,4-thioxane (TX), is proposed, which reinforces the stability of the fluorine-rich SEI. Moreover, the TX molecule has a strong affinity for coordinating with Zn 2+ and adsorbing at the electrode/electrolyte interface, thereby diminishing the activity of local water and consequently impeding SEI dissolution. The robust fluorine-rich SEI layer promotes the high durability of the zinc anode in repeated plating/stripping cycles, while concurrently suppressing HER and enhancing Coulombic efficiency. Notably, the symmetric cell with TX demonstrates exceptional electrochemical performance, sustaining over 500 hours at 20 mA cm -2 with 10 mAh cm -2 . Furthermore, the Zn||KVOH full cell exhibits excellent capacity retention, averaging 6.8 mAh cm -2 with 98 % retention after 400 cycles, even at high loading with a lean electrolyte. This work offers a novel perspective on SEI dissolution as a key factor in anode failure, providing valuable insights for the electrolyte design in energy storage devices., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Aloperine (ALO), a quinolizidine-type alkaloid isolated from a natural Chinese herb, has shown promising antitumor effects. Nevertheless, its common mechanism of action and specific target remain elusive. Here, it is demonstrated that ALO inhibits the proliferation and migration of non-small cell lung cancer cell lines in vitro and the tumor development in several mouse tumor models in vivo. Mechanistically, ALO inhibits the fusion of autophagosomes with lysosomes and the autophagic flux, leading to the accumulation of sequestosome-1 (SQSTM1) and production of reactive oxygen species (ROS), thereby inducing tumor cell apoptosis and preventing tumor growth. Knockdown of SQSTM1 in cells inhibits ROS production and reverses ALO-induced cell apoptosis. Furthermore, VPS4A is identified as a direct target of ALO, and the amino acids F153 and D263 of VPS4A are confirmed as the binding sites for ALO. Knockout of VPS4A in H1299 cells demonstrates a similar biological effect as ALO treatment. Additionally, ALO enhances the efficacy of the anti-PD-L1/TGF-β bispecific antibody in inhibiting LLC-derived subcutaneous tumor models. Thus, ALO is first identified as a novel late-stage autophagy inhibitor that triggers tumor cell death by targeting VPS4A., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Non-noble transition metal (TM)-based compounds have recently become a focal point of extensive research interest as electrocatalysts for the two electron oxygen reduction (2e - ORR) process. To efficiently drive this reaction, these TM-based electrocatalysts must bear unique physiochemical properties, which are strongly dependent on their phase structures. Consequently, adopting engineering strategies toward the phase structure has emerged as a cutting-edge scientific pursuit, crucial for achieving high activity, selectivity, and stability in the electrocatalytic process. This comprehensive review addresses the intricate field of phase engineering applied to non-noble TM-based compounds for 2e - ORR. First, the connotation of phase engineering and fundamental concepts related to oxygen reduction kinetics and thermodynamics are succinctly elucidated. Subsequently, the focus shifts to a detailed discussion of various phase engineering approaches, including elemental doping, defect creation, heterostructure construction, coordination tuning, crystalline design, and polymorphic transformation to boost or revive the 2e - ORR performance (selectivity, activity, and stability) of TM-based catalysts, accompanied by an insightful exploration of the phase-performance correlation. Finally, the review proposes fresh perspectives on the current challenges and opportunities in this burgeoning field, together with several critical research directions for the future development of non-noble TM-based electrocatalysts., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Flexible and stretchable electronics have attractive applications inaccessible to conventional rigid electronics. However, the mainstream transfer printing techniques have challenges for electronic films in terms of thickness and size and limitations for target substrates in terms of curvature, depth, and interfacial adhesion. Here a facile, damage-free, and contamination-free soap film transfer printing technique is reported that enables the wrinkle-free transfer of ultrathin electronic films, precise alignment in a transparent manner, and conformal and adhesion-independent printing onto various substrates, including those too topographically and adhesively challenging by existing methods. In principle, not only the pattern, resolution, and thickness of transferred films, but also the curvature, depth, and adhesion of target substrates are unlimited, while the size of transferred films can be as high as meter-scale. To demonstrate the capabilities of soap film transfer printing, pre-fabricated ultrathin electronics with multiple patterns, single micron resolution, sub-micron thickness, and centimeter size are conformably integrated onto the ultrathin web, ultra-soft cotton, DVD-R disk with the minimum radius of curvature of 131 nm, interior cavity of Klein bottle and dandelion with ultralow adhesion. The printed ultrathin sensors show superior conformabilities and robust adhesion, leading to engineering opportunities including electrocardiogram (ECG) signal acquisition and temperature measurement in aqueous environments., (© 2023 Wiley‐VCH GmbH.)

N-doped carbon (NC)-encapsulated transition metal (TM) nanocomposites are considered as alternatives to Pt-based hydrogen evolution reaction (HER) electrocatalysts; however, their poor electron transfer and mass diffusion capability at high current densities hinder their practical application. Herein, an oriented coupling strategy for the in situ grafting of ultrafine Co nanoparticle-embedded hollow porous C polyhedra onto Si nanowires (Co/NC-HP@Si-NWs) is proposed to address this concern. Experimental investigations reveal that the intimate coupling between the Si-NW and Co/NC nanocage forms a multithreaded conductive network, lowering the energy barrier for internal electron transfer. When functionalized as an HER electrocatalyst in 0.5 m H 2 SO 4 , Co/NC-HP@Si-NWs deliver overpotentials as low as 57 and 440 mV at 10 and 500 mA cm -2 , respectively, which are much better than those of the pristine Co/NC-HP. Moreover, Co/NC-HP@Si-NWs show an outstanding cycle durability of 24 h at 10 and 500 mA cm -2 . The findings of this study are expected to inspire revolutionary work on the development of Si-mediated TM-based electrocatalysts for the HER., (© 2023 Wiley-VCH GmbH.)

Recent developed interfacial solar brine crystallizers, which employ solar-driven water evaporation for salts crystallization from the near-saturation brine to achieve zero liquid discharge (ZLD) brine treatment, are promising due to their excellent energy efficiency and sustainability. However, most existing interfacial solar crystallizers are only tested using NaCl solution and failed to maintain high evaporation capability when treating real seawater due to the scaling problem caused by the crystallization of high-valent cations. Herein, an artificial tree solar crystallizer (ATSC) with a multi-branched and interconnected open-cell cellular structure that significantly increased evaporation surface is rationally designed, achieving an ultra-high evaporation rate (2.30 kg m -2  h -1 during 2 h exposure) and high energy efficiency (128%) in concentrated real seawater. The unit cell design of ATSC promoted salt crystallization on the outer frame rather than the inner voids, ensuring that salt crystallization does not affect the continuous transport of brine through the pores inside the unit cell, thus ATSC can maintain a stable evaporation rate of 1.94 kg m -2  h -1 on average in concentrated seawater for 80 h continuous exposure. The design concept of ATSC represents a major step forward toward ZLD treatment of high-salinity brine in many industrial processes is believed., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Simultaneously achieving high efficiency and robust device stability remains a significant challenge for organic solar cells (OSCs). Solving this challenge is highly dependent on the film morphology of the bulk heterojunction (BHJ) photoactive blends; however, there is a lack of rational control strategy. Herein, it is shown that the molecular crystallinity and nanomorphology of nonfullerene-based BHJ can be effectively controlled by a squaraine-based doping strategy, leading to an increase in device efficiency from 17.26% to 18.5% when doping 2 wt% squaraine into the PBDB-TF:BTP-eC9:PC 71 BM ternary BHJ. The efficiency is further improved to 19.11% (certified 19.06%) using an indium-tin-oxide-free column-patterned microcavity (CPM) architecture. Combined with interfacial modification, CPM quaternary OSC excitingly shows an extrapolated lifetime of ≈23 years based on accelerated aging test, with the mechanism behind enhanced stability well studied. Furthermore, a flexible OSC module with a high and stable efficiency of 15.2% and an overall area of 5 cm 2 is successfully fabricated, exhibiting a high average output power for wearable electronics. This work demonstrates that OSCs with new design of BHJ and device architecture are highly promising to be practical relevance with excellent performance and stability., (© 2023 Wiley-VCH GmbH.)

Metal oxides with diverse compositions and structures have garnered considerable interest from researchers in various reactions, which benefits from transmission electron microscopy (TEM) in determining their morphologies, phase, structural and chemical information. Recent breakthroughs have made liquid-phase TEM a promising imaging platform for tracking the dynamic structure, morphology, and composition evolution of metal oxides in solution under work conditions. Herein, this review introduces the recent advances in liquid cells, especially closed liquid cell chips. Subsequently, the recent progress including particle growth, phase transformation, self-assembly, core-shell nanostructure growth, and chemical etching are introduced. With the late technical advances in TEM and liquid cells, liquid-phase TEM is used to characterize many fundamental processes of metal oxides for CO 2 reduction and water-splitting reactions. Finally, the outlook and challenges in this research field are discussed. It is believed this compilation inspires and stimulates more efforts in developing and utilizing in situ liquid-phase TEM for metal oxides at the atomic scale for different applications., (© 2023 Wiley-VCH GmbH.)

Vacancy defect engineering has been well leveraged to flexibly shape comprehensive physicochemical properties of diverse catalysts. In particular, growing research effort has been devoted to engineering chalcogen anionic vacancies (S/Se/Te) of 2D transition metal dichalcogenides (2D TMDs) toward the ultimate performance limit of electrocatalytic hydrogen evolution reaction (HER). In spite of remarkable progress achieved in the past decade, systematic and in-depth insights into the state-of-the-art vacancy engineering for 2D-TMDs-based electrocatalysis are still lacking. Herein, this review delivers a full picture of vacancy engineering evolving from aggregated to atomic configurations covering their development background, controllable manufacturing, thorough characterization, and representative HER application. Of particular interest, the deep-seated correlations between specific vacancy regulation routes and resulting catalytic performance improvement are logically clarified in terms of atomic rearrangement, charge redistribution, energy band variation, intermediate adsorption-desorption optimization, and charge/mass transfer facilitation. Beyond that, a broader vision is cast into the cutting-edge research fields of vacancy-engineering-based single-atom catalysis and dynamic structure-performance correlations across catalyst service lifetime. Together with critical discussion on residual challenges and future prospects, this review sheds new light on the rational design of advanced defect catalysts and navigates their broader application in high-efficiency energy conversion and storage fields., (© 2023 Wiley-VCH GmbH.)

Multifunctional electronic skins (e-skins) that can sense various stimuli have demonstrated increasing potential in many fields. However, most e-skins are human-oriented that cannot work in hash environments such as high temperature, underwater, and corrosive chemicals, impairing their applications, especially in human-machine interfaces, intelligent machines, robotics, and so on. Inspired by the crack-shaped sensory organs of spiders, an environmentally robust and ultrasensitive multifunctional e-skin is developed. By developing a polyimide-based metal crack-localization strategy, the device has excellent environment adaptability since polyimide has high thermal stability and chemical durability. The localized cracked part serves as an ultrasensitive strain sensing unit, while the non-cracked serpentine part is solely responsible for temperature. Since the two units are made of the same material and process, the signals are decoupled easily. The proposed device is the first multifunctional e-skin that can be used in harsh environments, therefore is of great potential for both human and robot-oriented applications., (© 2023 Wiley-VCH GmbH.)

Doxorubicin-induced cardiomyopathy (DIC) brings tough clinical challenges as well as continued demand in developing agents for adjuvant cardioprotective therapies. Here, a zebrafish phenotypic screening with deep-learning assisted multiplex cardiac functional analysis using motion videos of larval hearts is established. Through training the model on a dataset of 2125 labeled ventricular images, ZVSegNet and HRNet exhibit superior performance over previous methods. As a result of high-content phenotypic screening, cyanidin chloride (CyCl) is identified as a potent suppressor of DIC. CyCl effectively rescues cardiac cell death and improves heart function in both in vitro and in vivo models of Doxorubicin (Dox) exposure. CyCl shows strong inhibitory effects on lipid peroxidation and mitochondrial damage and prevents ferroptosis and apoptosis-related cell death. Molecular docking and thermal shift assay further suggest a direct binding between CyCl and Keap1, which may compete for the Keap1-Nrf2 interaction, promote nuclear accumulation of Nrf2, and subsequentially transactivate Gpx4 and other antioxidant factors. Site-specific mutation of R415A in Keap1 significantly attenuates the protective effects of CyCl against Dox-induced cardiotoxicity. Taken together, the capability of deep-learning-assisted phenotypic screening in identifying promising lead compounds against DIC is exhibited, and new perspectives into drug discovery in the era of artificial intelligence are provided., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Metal-organic frameworks (MOFs) are regarded as one promising class of precatalysts for electrocatalytic oxygen evolution reaction (OER), yet most of them suffer from poor conductivity and lack of coordinatively unsaturated metal sites, which hinders the fast electrochemical reconstruction and thus a poor OER activity. To address this issue, a unique heterocomposite has been constructed by in situ inserting carbon dots (CDs) into cobalt-based zeolitic imidazolate framework (Co-ZIF) nanosheet arrays (Co-ZIF/CDs/CC) in the presence of carbon cloth (CC) via one-pot coprecipitation for alkaline OER. Benefiting from the synergism between CDs and Co-ZIF subunits such as superior conductivity, strong charge interaction as well as abundant metal sites exposure, the Co-ZIF/CDs/CC exhibits an enhanced promotion effect for OER and contributes to the deep phase transformation from CDs-coupled Co-ZIF to CDs-coupled active CoOOH. As expected, the achieved Co-ZIF/CDs/CC only requires an overpotential of 226 mV to deliver 10 mA cm -2 in 1.0 M KOH, which is lower than that of Co-ZIF/CC and superior to most previously reported CC-supported MOF precatalysts. Moreover, it can also maintain a large current density of 100 mA cm -2 for 24 h with negligible activity decay., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Carbon dots (CDs) with good water solubility and biocompatibility have become a research hotspot in the nano-enzyme and biomedical field. However, the problems of low catalytic activity and ambiguous catalytic site of CDs as nanozymes still need to be addressed. In this work, CDs loaded with Cu single atoms are obtained through pyrolysis, and the coordination structure and surface functional groups are regulated by adjusting the pyrolysis temperature. CDs obtained at 300 °C (named Cu-CDs-300) have the most carboxyl content and Cu is coordinated in the form of CuN 2 O 2 , which can better decompose H 2 O 2 to produce free radical and is beneficial to catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). The v max is 6.56*10 -7  m s -1 , 6.56 times higher than that of horseradish peroxidase (HRP). Moreover, Cu-CDs-300 can effectively lead to CT26 apoptosis by generating much free radicals. This work demonstrates the synergistic effect of oxygen-containing functional groups and metal coordination structures on peroxide-like activity of CDs and provides new ideas for the design of clear active structure and high efficiency peroxide-like single atom CDs catalyst., (© 2023 Wiley-VCH GmbH.)

Nanoscale drug carriers play a crucial role in reducing side effects of chemotherapy drugs. However, the mononuclear phagocyte system (MPS) and the drug protonation after nanoparticles (NPs) burst release still limit the drug delivery efficiency. In this work, a self-disguised Nanospy is designed to overcome this problem. The Nanospy is composed of: i) poly (lactic-co-glycolic acid)-polyethylene glycol (PLGA-PEG) loading doxorubicin is the core structure of the Nanospy. ii) CD47 mimic peptides (CD47p) is linked to NPs which conveyed the "don't eat me" signal. iii) 4-(2-aminoethyl) benzenesulfonamide (AEBS) as the inhibitor of Carbonic anhydrase IX (CAIX) linked to NPs. Briefly, when the Nanospy circulates in the bloodstream, CD47p binds to the regulatory protein α (SIRPα) on the surface of macrophages, which causes the Nanospy escapes from phagocytosis. Subsequently, the Nanospy enriches in tumor and the AEBS reverses the acidic microenvironment of tumor. Due to above characteristics, the Nanospy reduces liver macrophage phagocytosis by 25% and increases tumor in situ DOX concentration by 56% compared to PLGA@DOX treatment. In addition, the Nanospy effectively inhibits tumor growth with a 63% volume reduction. This work presents a unique design to evade the capture of MPS and overcomes the influence of acidic tumor microenvironment (TME) on weakly alkaline drugs., (© 2023 Wiley-VCH GmbH.)

Electrochemical two-electron oxygen reduction reaction (2 e - ORR) to produce hydrogen peroxide (H 2 O 2 ) is a promising alternative to the energetically intensive anthraquinone process. However, there remain challenges in designing 2 e - ORR catalysts that meet the application criteria. Here, we successfully adopt a microwave-assisted mechanochemical-thermal approach to synthesize hexagonal phase SnO 2 (h-SnO 2 ) nanoribbons with largely exposed edge structures. In 0.1 M Na 2 SO 4 electrolyte, the h-SnO 2 catalysts achieve the excellent H 2 O 2 selectivity of 99.99 %. Moreover, when employed as the catalyst in flow cell devices, they exhibit a high yield of 3885.26 mmol g -1  h -1 . The enhanced catalytic performance is attributed to the special crystal structure and morphology, resulting in abundantly exposed edge active sites to convert O 2 to H 2 O 2 , which is confirmed by density functional theory calculations., (© 2023 Wiley-VCH GmbH.)

Benzyl alcohol (BnOH) is a widely-used preservative in a variety of cosmetics, but the excess addition (≥1.0 %) may cause strong symptoms such as nausea, gastrointestinal irritation, convulsion, even death, making it crucial to monitor and control the addition quantity. Herein, we have developed a test-strip-like BnOH detection method via tailoring a galactose oxidase (GOase) towards BnOH oxidation and preparing a self-powered electrochromic strip for BnOH concentration visualization. A double-substituted GOase variant (Y329S/R330F), on the basis of the reported GOase M 1 , has been obtained by semi-rational design with a 24.6-fold improved activity towards BnOH compared to GOase M 1 . The GOase Y329S/R330F electrode has a response to BnOH with a linear range of 0.04 to 3.25 mM (R 2 =0.9985), a sensitivity of 122.78 μA mM -1  cm -2 , and a detection limit of 0.03 mM (S/N=3). Coupling an electrochromic Prussian blue (PB) cathode helps the successful sensing visualization without any further power supply. The present sensing is more convenient and user-friendly than the generally used gas chromatography (GC) and high performance liquid chromatography (HPLC), and brings a more accessible solution to the field of quality controlling., (© 2023 Wiley-VCH GmbH.)

Current treatments for infections caused by multidrug-resistant bacteria still remain challenging and therapeutic materials with high efficacy are of demand. Herein, a bactericidal nanocomposite was constructed by loading Roxarsone (ROX) onto nitrosylated mesoporous polydopamine (named mPDA@NO-ROX). The designed nanocomposite exhibited considerable photothermal effect and controlled NO and ROX co-delivery under the irradiation of near-infrared laser (NIR) to achieve enhanced chemo-photothermal antibacterial therapy. The in vitro antibacterial evaluation of the mPDA@NO-ROX demonstrated the effective elimination of the Gram-negative tetracycline-resistant Escherichia coil and Gram-positive methicillin-resistant Staphylococcus aureus under mild NIR irradiation compared to merely ROX loaded unmodified mPDA, indicating the NO enhanced chemo-photothermal therapy. In addition, the cytotoxicity experiments indicated that mPDA@NO-ROX exhibited only 5 % of hemolysis rate and high cell viability at 1 mg mL -1 against mammalian fibroblasts, suggesting the excellent biocompatibility. In conclusion, the mPDA@NO-ROX could be a promising candidate for anti-infection therapy of multidrug-resistant bacteria., (© 2023 Wiley-VCH GmbH.)

A hydrogen processing strategy is developed to enable bulk LaNi 5 to attain high activity and long-term stability toward the electrocatalytic oxygen evolution reaction (OER). By a combination of in situ Raman and quasi in situ X-ray absorption (XAS) spectra, secondary-electron-excited scanning transmission electron microscopy (STEM) patterns as well as the Rietveld method and density functional theory (DFT) calculations, it is discovered that hydrogen-induced lattice distortion, grain refinement, and particle cracks dictate the effective reconstruction of the LaNi 5 surface into a porous hetero-nanoarchitecture composed of uniformly confined active γ-NiOOH nanocrystals by La(OH) 3 layer in the alkaline OER process. This significantly optimizes the charge transfer, structural integrity, active-site exposure, and adsorption energy toward the reaction intermediates. Benefiting from these merits, the overpotential (322 mV) at 100 mA cm -2 for the hydrogen-processed OER catalyst deposited on nickel foam is reduced by 104 mV as compared to the original phase. Notably, it exhibits remarkable stability for 10 days at an industrial-grade current density of more than 560 mA cm -2 in alkaline media., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Although CsPbI 3 perovskites have shown tremendous potential in the photovoltaic field owing to their excellent thermal stability, the device performance is seriously restricted by severe photovoltage loss. The buried titanium oxide/perovskite interface plays a critical role in interfacial charge transport and perovskite crystallization, which is closely related to open-circuit voltage deficit stemming from nonradiative recombination. Herein, target molecules named 3-sulphonatopropyl acrylate potassium salts are deliberately employed with special functional groups for modifying the buried interface, giving rise to favorable functions in terms of passivating interfacial defects, optimizing energetic alignment, and facilitating perovskite crystallization. Experimental characterizations and theoretical calculations reveal that the buried interface modification inhibits the electron transfer barrier and simultaneously improves perovskite crystal quality, thereby reducing trap-assisted charge recombination and interfacial energetic loss. Consequently, the omnibearing modification regarding the buried interface endows the devices with an impressive efficiency of 20.98%, achieving a record-low V OC deficit of 0.451 V. The as-proposed buried interface modification strategy renders with a universal prescription to push the limit of V OC deficit, showing a promising future in developing high-performance all-inorganic perovskite photovoltaics., (© 2022 Wiley-VCH GmbH.)

Biological barriers significantly limit the delivery efficiency of drug delivery systems, resulting in undesired therapeutic effects. When designing a delivery system with optimized penetration behavior across the biological barriers, mechanical properties, such as deformability, are emerging as important parameters that need to be considered, although they are usually neglected in current research. Herein, a liquid core nanoparticle (LCN) composed of a polymer-encapsulated edible oil droplet is demonstrated. Owing to the unique structure in which the liquid oil core is encapsulated by a layer of highly hydrophilic and cross-linked polymer, the LCN exhibits high mechanical softness, making it deformable under external forces. With high deformability, LCNs can effectively penetrate through several important biological barriers including deep tumor tissue, blood-brain barriers, mucus layers, and bacterial biofilms. Moreover, the potential of the LCN as a drug delivery system is also demonstrated by the loading and release of several clinical drugs. With the capability of penetrating biological barriers and delivering drugs, LCN provides a potential platform for disease treatments, particularly for those suffering from inadequate drug penetration., (© 2022 Wiley-VCH GmbH.)

Vacancy engineering is deemed as one of the powerful protocols to tune the catalytic activity of electrocatalysts. Herein, Se-vacancy with charge polarization is created in the NiSe 2 structure (NiSe 2 -V Se ) via a sequential phase conversion strategy. By a combined analysis of the Rietveld method, transient photovoltage spectra (TPV), in situ Raman and density functional theory (DFT) calculation, it is unequivocally discovered that the presence of charge-polarized Se-vacancy is beneficial for stabilizing the structure, decreasing the electron transfer kinetics, as well as optimizing the free adsorption energy of reaction intermediate during two-electron oxygen reduction reaction (2e - ORR). Benefiting from these merits, the as-prepared NiSe 2 -V Se delivered the highest selectivity of 96% toward H 2 O 2 in alkaline media, together with a selectivity higher than 90% over the wide potential range from 0.25 to 0.55 V, ranking it in the top level among the previously reported transition metal-based electrocatalysts. Most notably, it also displayed admirable stability with only a slight selectivity decay after 5000 cycles of accelerated degradation test (ADT)., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

π electron configuration plays a pivotal role in metal-free carbon catalysts, and its delocalization degree overwhelmingly dominates catalytic activity. However, precise and targeted regulation of inherent π electrons still remain challenging. Here, one chemical-bond-targeted physical clipping strategy is proposed and effectively adopted in the cutting-edge carbon material system of graphdiyne (GDY) as a concept-of-proof. The delocalized electrons are expected to be periodically reformatted for substantially enhancing π electron delocalization. Via theoretical screening and well-designed experiments, periodical interruption of Csp-Csp 2 bonds in GDY can render sp-C sites with decent activity, ultimately yielding top-ranking electrocatalytic performance without intentionally introducing external decoration. The as-proposed concept endows a universal prescription to push the limit of delocalization degree, thus shedding novel light on the rational design of decent metal-free catalysts., (© 2022 Wiley-VCH GmbH.)

Positively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state-of-the-art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe-PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X-ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni-based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H + , while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe-PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm -2 and exhibits a high mass activity of 10.93 A mg Pt -1 (at 100 mV). Most importantly, it only needs an ultra-low overpotential of 193 mV to achieve a high current density of 1000 mA cm -2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large-scale industrial application in the future., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Extracellular matrix (ECM) is crucial in various biological functions during tumor progression, including induction of anoikis resistance and cell adhesion-mediated drug resistance (CAM-DR). Fibronectin (FN) is a vital ECM component with direct regulatory effects on ECM-mediated anoikis resistance and CAM-DR, making it an attractive and innovative therapeutic target for depriving ECM in tumor tissue. Herein, an ECM deprivation system (EDS) is developed based on FN targeting self-assembly peptide for constructing nanofibers in the ECM of renal cell carcinoma (RCC), which contributes to: i) targeting and recognizing FN to form nanofibers for long-term retention in ECM, ii) reversing anoikis resistance via arresting the FN signaling pathway, and iii) serving as a drug-loading platform for sensitizing chemotherapy by ameliorating CAM-DR. The results reveal that EDS significantly reverses anoikis resistance of RCC cells by inhibiting the phosphorylation of FAK, a positive regulator of the FN signaling pathway. Meanwhile, EDS serves as a chemotherapy-sensitizer of cancer, exerting significant synergistic effects with doxorubicin (DOX). In vivo validation experiments show that EDS effectively suppresses metastasis and tumor growth with chemotherapy resistance. Collectively, the innovative EDS notably inhibits the tumor-promoting effect of ECM and may provide a novel approach for suppressing ECM and enhancing chemo-drug sensitivity., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Developing advanced electrocatalysts with exceptional two electron (2e - ) selectivity, activity, and stability is crucial for driving the oxygen reduction reaction (ORR) to produce hydrogen peroxide (H 2 O 2 ). Herein, a composition engineering strategy is proposed to flexibly regulate the intrinsic activity of amorphous nickel boride nanoarchitectures for efficient 2e - ORR by oriented reduction of Ni 2+ with different amounts of BH 4 - . Among borides, the amorphous NiB 2 delivers the 2e - selectivity close to 99% at 0.4 V and over 93% in a wide potential range, together with a negligible activity decay under prolonged time. Notably, an ultrahigh H 2 O 2 production rate of 4.753 mol g cat -1 h -1 is achieved upon assembling NiB 2 in the practical gas diffusion electrode. The combination of X-ray absorption and in situ Raman spectroscopy, as well as transient photovoltage measurements with density functional theory, unequivocally reveal that the atomic ratio between Ni and B induces the local electronic structure diversity, allowing optimization of the adsorption energy of Ni toward *OOH and reducing of the interfacial charge-transfer kinetics to preserve the OO bond., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Ultrathin 2D semiconductor devices are considered to have beyond-silicon potential but are severely troubled by the high Schottky barriers of the metal-semiconductor contacts, especially for p-type semiconductors. Due to the severe Fermi-level pinning effect and the lack of conventional semimetals with high work functions, their Schottky hole barriers are hardly removed. Here, an all-van-der-Waals barrier-free hole contact between p-type tellurene semiconductor and layered 1T'-WS 2 semimetal is reported, which achieves a zero Schottky barrier height of 3 ± 9 meV and a high field-effect mobility of ≈1304 cm 2 V -1 s -1 . The formation of such contacts can be attributed to the higher work function of ≈4.95 eV of the 1T'-WS 2 semimetal, which is in sharp contrast with low work function (4.1-4.7 eV) of conventional semimetals. The study defines an available strategy for eliminating the Schottky barrier of metal-semiconductor contacts, facilitating 2D-semiconductor-based electronics and optoelectronics to extend Moore's law., (© 2022 Wiley-VCH GmbH.)

Active species regulation is a key scientific issue that essentially determines the selectivity and activity of a photocatalyst. Herein, Cu I -bridged tetrakis(4-ethynylphenyl)ethene aggregates (T 4 EPE-Cu) with photo-regulated 1 O 2 and O 2 .- generation were demonstrated for selective photocatalytic aerobic oxidation. In this system, transient photovoltage combined with the density functional theory calculations confirmed that Cu-alkynyl was the main oxygen activation site. The adsorbed O 2 tends to produce O 2 .- because of the potential well effect of Cu-alkynyl under high-energy light excitation. But under low-energy light, O 2 tends to produce 1 O 2 via resonance energy transfer with Cu-alkynyl. For α-terpinene oxidation, the ratios of 1 O 2 products to O 2 .- products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T 4 EPE-Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %., (© 2022 Wiley-VCH GmbH.)

Efficient delivery of biomacromolecules or drugs across the cell membrane via endocytosis usually encounters inevitable entrapment in endosomes and subsequent degradation in lyso-endosomes. To address this issue, a series of arginine-rich cell penetrating polymers is designed and synthesized, which internalize into cells by inducing the formation of pores on the cell membrane, thereby crossing the cell membrane via direct translocation that fundamentally avoids endo/lysosomal entrapment. The structure-activity relationship studies show that PTn-R2-C6, which is a type of polymer that has two arginine residues and a flexible hexanoic acid linker in each side chain, exhibits excellent pore-formation ability on the cell membrane. Further investigations indicate that PTn-R2-C6 rapidly transports plasmid DNAs into cytosol through a similar endocytosis-independent pathway, thereby achieving significantly higher transfection efficiency and lower cytotoxicity than the gold-standard transfection reagent PEI 25K. These results suggest the great potential of PTn-R2-C6 as a safe and efficient gene transfection reagent for wide applications including disease treatments, vaccine development, and biomedical research purposes., (© 2022 Wiley-VCH GmbH.)

Antimicrobial peptides (AMPs) hold great potential for use in tumor treatment. However, developing AMP-based antitumor therapies is challenging due to circulatory instability, hemolytic toxicity, low selectivity, and poor cell permeability of AMPs. In this study, a polymeric carrier for AMPs (denoted as PAMP m -co-PPBE n /PCA) is presented that effectively enhances their anticancer efficacy while minimizing their potential side effects. By integrating multiple responsive structures at the molecular level, the carrier finely controls the spatial distribution of AMPs in different biological microenvironments, thereby effectively modulating their membranolytic ability. Upon employing KLA as the model AMP, the polymeric carrier's hemolytic toxicity during blood circulation is suppressed, its cellular internalization when reaching tumor tissues facilitated, and its membranolytic toxicity toward the mitochondria upon entering cancer cells restored and further enhanced. Animal studies indicate that this approach significantly improves the antitumor efficacy of KLA and reduces its toxicity. Considering that the loading method for most AMPs is identical to that of KLA, the polymeric carrier reported in this study may provide a feasible approach for the development of AMP-based cancer treatments., (© 2022 Wiley-VCH GmbH.)

The electrochemical oxygen reduction reaction (ORR) offers a most promising and efficient route to produce hydrogen peroxide (H 2 O 2 ), yet the lack of cost-effective and high-performance electrocatalysts have restricted its practical application. Herein, an entropy-enhancement strategy has been employed to enable the low-cost perovskite oxide to effectively catalyze the electrosynthesis of H 2 O 2 . The optimized Pb(NiWMnNbZrTi) 1/6 O 3 ceramic is available on a kilogram-scale and displays commendable ORR activity in alkaline media with high selectivity over 91 % across the wide potential range for H 2 O 2 including an outstanding degradation property for organic dyes through the Fenton process. The exceptional performance of this perovskite oxide is attributed to the entropy stabilization-induced polymorphic transformation assuring the robust structural stability, decreased charge mobility as well as synergistic catalytic effects which we confirm using advanced in situ Raman, transient photovoltage, Rietveld refinement as well as finite elemental analysis., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Transition metals, in particular noble metals, are the most common species in metal-mediated water electrolysis because they serve as highly active catalytic sites. In many cases, the presence of nontransition metals, that is, s-, p-, and f-block metals with high natural abundance in the earth-crust in the catalytic material is indispensable to boost efficiency and durability in water electrolysis. This is why alkali metals, alkaline-earth metals, rare-earth metals, lean metals, and metalloids receive growing interest in this research area. In spite of the pivotal role of these nontransition metals in tuning efficiency of water electrolysis, there is far more room for developments toward a knowledge-based catalyst design. In this review, five classes of nontransition metals species which are successfully utilized in water electrolysis, with special emphasis on electronic structure-catalytic activity relationships and phase stability, are discussed. Moreover, specific fundamental aspects on electrocatalysts for water electrolysis as well as a perspective on this research field are also addressed in this account. It is anticipated that this review can trigger a broader interest in using s-, p-, and f-block metals species toward the discovery of advanced polymetal-containing electrocatalysts for practical water splitting., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Piezoelectric nanocomposites with oxide fillers in a polymer matrix combine the merit of high piezoelectric response of the oxides and flexibility as well as biocompatibility of the polymers. Understanding the role of the choice of materials and the filler-matrix architecture is critical to achieving desired functionality of a composite towards applications in flexible electronics and energy harvest devices. Herein, a high-throughput phase-field simulation is conducted to systematically reveal the influence of morphology and spatial orientation of an oxide filler on the piezoelectric, mechanical, and dielectric properties of the piezoelectric nanocomposites. It is discovered that with a constant filler volume fraction, a composite composed of vertical pillars exhibits superior piezoelectric response and electromechanical coupling coefficient as compared to the other geometric configurations. An analytical regression is established from a linear regression-based machine learning model, which can be employed to predict the performance of nanocomposites filled with oxides with a given set of piezoelectric coefficient, dielectric permittivity, and stiffness. This work not only sheds light on the fundamental mechanism of piezoelectric nanocomposites, but also offers a promising material design strategy for developing high-performance polymer/inorganic oxide composite-based wearable electronics., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Rubidium cation (Rb + ) addition is witnessed to play a pivotal role in boosting the comprehensive performance of organic-inorganic hybrid perovskite solar cells. However, the origin of such success derived from irreplaceable superiorities brought by Rb + remains ambiguous. Herein, grain-boundary-including atomic models are adopted for the accurate theoretical analysis of practical Rb + distribution in perovskite structures. The spatial distribution, covering both the grain interiors and boundaries, is thoroughly identified by virtue of synchrotron-based grazing-incidence X-ray diffraction. On this basis, the prominent elevation of the halogen vacancy formation energy, improved charge-carrier dynamics, and the electronic passivation mechanism in the grain interior are expounded. As evidenced by the increased energy barrier and suppressed microcurrent, the critical role of Rb + addition in blocking the diffusion pathway along grain boundaries, inhibiting halide phase segregation, and eventually enhancing intrinsic stability is elucidated. Hence, the linkage avalanche effect of occupied location dominated by subtle changes in Rb + concentration on electronic defects, ion migration, and phase stability is completely investigated in detail, shedding a new light on the advancement of high-efficiency cascade-incorporating strategies and perovskite compositional engineering., (© 2022 Wiley-VCH GmbH.)

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ≈97% Ir catalyst and augmenting a catalyst utilization to ≈24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. It is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes., (© 2022 Wiley-VCH GmbH.)