Asymmetric Cu(I)─W Dual-Atomic Sites Enable C─C Coupling for Selective Photocatalytic CO2 Reduction to C2H4.

Solar-driven CO2 reduction into value-added C2+ chemical fuels, such as C2H4, is promising in meeting the carbon-neutral future, yet the performance is usually hindered by the high energy barrier of the C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms-modified W18O49 nanowires (Cu1/W18O49) photocatalyst with asymmetric Cu─W dual sites is reported for selective photocatalytic CO2 reduction to C2H4. The interconversion between W(V) and W(VI) in W18O49 ensures the stability of Cu(I) during the photocatalytic process. Under light irradiation, the optimal Cu1/W18O49 (3.6-Cu1/W18O49) catalyst exhibits concurrent high activity and selectivity toward C2H4 production, reaching a corresponding yield rate of 4.9 µmol g-1 h-1 and selectivity as high as 72.8%, respectively. Combined in situ spectroscopies and computational calculations reveal that Cu(I) single atoms stabilize the *CO intermediate, and the asymmetric Cu─W dual sites effectively reduce the energy barrier for the C─C coupling of two neighboring CO intermediates, enabling the highly selective C2H4 generation from CO2 photoreduction. This work demonstrates leveraging stabilized atomically-dispersed Cu(I) in asymmetric dual-sites for selective CO2-to-C2H4 conversion and can provide new insight into photocatalytic CO2 reduction to other targeted C2+ products through rational construction of active sites for C─C coupling.

Wafer Scale Gallium Nitride Integrated Electrode Toward Robust High Temperature Energy Storage.

Gallium Nitride (GaN), as the representative of wide bandgap semiconductors, has great prospects in accomplishing rapid charge delivery under high-temperature environments thanks to excellent structural stability and electron mobility. However, there is still a gap in wafer-scale GaN single-crystal integrated electrodes applied in the energy storage field. Herein, Si-doped GaN nanochannel with gallium oxynitride (GaON) layer on a centimeter scale (denoted by GaN NC) is reported. The Si atoms modulate electronic redistribution to improve conductivity and drive nanochannel formation. Apart from that, the distinctive nanochannel configuration with a GaON layer provides adequate active sites and extraordinary structural stability. The GaN-based supercapacitors are assembled and deliver outstanding charge storage capabilities at 140 °C. Surprisingly, 90% retention is maintained after 50 000 cycles. This study opens the pathway toward wafer-scale GaN single-crystal integrated electrodes with self-powered characteristics that are compatible with various (opto)-electronic devices.

Ordered Vacancies as Sodium Ion Micropumps in Cu-Deficient Copper Indium Diselenide to Enhance Sodium Storage.

Unordered vacancies engineered in host anode materials cannot well maintain the uniform Na+ adsorbed and possibly render the local structural stress intense, resulting in electrode peeling and battery failure. Here, the indium is first introduced into Cu2Se to achieve the formation of CuInSe2. Next, an ion extraction strategy is employed to fabricate Cu0.54In1.15Se2 enriched with ordered vacancies by spontaneous formation of defect pairs. Such ordered defects, compared with unordered ones, can serve as myriad sodium ion micropumps evenly distributing in crystalline host to homogenize the adsorbed Na+ and the generated volumetric stress during the electrochemistry. Furthermore, Cu0.54In1.15Se2 is indeed proved by the calculations to exhibit smaller volumetric variation than the counterpart with unordered vacancies. Thanks to the distinct ordered vacancy structure, the material exhibits a highly reversible capacity of 428 mAh g-1 at 1 C and a high-rate stability of 311.7 mAh g-1 at 10 C after 5000 cycles when employed as an anode material for Sodium-ion batteries (SIBs). This work presents the promotive effect of ordered vacancies on the electrochemistry of SIBs and demonstrates the superiority to unordered vacancies, which is expected to extend it to other metal-ion batteries, not limited to SIBs to achieve high capacity and cycling stability.

Unveiling pH-Dependent Adsorption Strength of *CO2 - Intermediate over High-Density Sn Single Atom Catalyst for Acidic CO2-to-HCOOH Electroreduction.

The acidic electrochemical CO2 reduction reaction (CO2RR) for direct formic acid (HCOOH) production holds promise in meeting the carbon-neutral target, yet its performance is hindered by the competing hydrogen evolution reaction (HER). Understanding the adsorption strength of the key intermediates in acidic electrolyte is indispensable to favor CO2RR over HER. In this work, high-density Sn single atom catalysts (SACs) were prepared and used as catalyst, to reveal the pH-dependent adsorption strength and coverage of *CO2 - intermediatethat enables enhanced acidic CO2RR towards direct HCOOH production. At pH=3, Sn SACs could deliver a high Faradaic efficiency (90.8 %) of HCOOH formation and a corresponding partial current density up to -178.5 mA cm-2. The detailed in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic studies reveal that a favorable alkaline microenvironment for CO2RR to HCOOH is formed near the surface of Sn SACs, even in the acidic electrolyte. More importantly, the pH-dependent adsorption strength of *CO2 - intermediate is unravelled over the Sn SACs, which in turn affects the competition between HER and CO2RR in acidic electrolyte.

Ir Single Atoms Boost Metal-Oxygen Covalency on Selenide-Derived NiOOH for Direct Intramolecular Oxygen Coupling.

This investigation probes the intricate interplay of catalyst dynamics and reaction pathways during the oxygen evolution reaction (OER), highlighting the significance of atomic-level and local ligand structure insights in crafting highly active electrocatalysts. Leveraging a tailored ion exchange reaction followed by electrochemical dynamic reconstruction, we engineered a novel catalytic structure featuring single Ir atoms anchored to NiOOH (Ir1@NiOOH). This novel approach involved the strategic replacement of Fe with Ir, facilitating the transition of selenide precatalysts into active (oxy)hydroxides. This elemental substitution promoted an upward shift in the O 2p band and intensified the metal-oxygen covalency, thereby altering the OER mechanism toward enhanced activity. The shift from a single-metal site mechanism (SMSM) in NiOOH to a dual-metal-site mechanism (DMSM) in Ir1@NiOOH was substantiated by in situ differential electrochemical mass spectrometry (DEMS) and supported by theoretical insights. Remarkably, the Ir1@NiOOH electrode exhibited exceptional electrocatalytic performance, achieving overpotentials as low as 142 and 308 mV at current densities of 10 and 1000 mA cm-2, respectively, setting a new benchmark for the electrocatalysis of OER.

Structure and Charge Carrier Separation Promotion Effects of Antiphase Boundaries in Cesium Lead Bromide.

Defects in lead halide perovskites (LHPs) may have a significant impact on charge carrier separation, but the roles of the defects are not fully understood. Here, using aberration-corrected scanning transmission electron microscopy (STEM), different types of antiphase boundaries (APBs) are discovered in CsPbBr3 platelets. APBs with a displacement vector of 1/4[111] are characterized by double layers of CsBr layers at the (110) or (001) planes, while APBs at the (112) planes are formed through edge sharing of PbBr6 ̵octahedra. Significant lattice distortions are determined at (001) and (110) APBs on the basis of quantitative analyses of STEM images. Density functional theory calculations demonstrate that all three types of APBs can induce band offsets at their valence bands and conduction bands. The APBs are intended to promote the separation of photogenerated charge carriers in LHPs. These findings provide a crystal engineering technique for enhancing the optoelectronic properties of LHPs by controlling defects.

Robust links in photoactive covalent organic frameworks enable effective photocatalytic reactions under harsh conditions.

Developing heterogeneous photocatalysts for the applications in harsh conditions is of high importance but challenging. Herein, by converting the imine linkages into quinoline groups of triphenylamine incorporated covalent organic frameworks (COFs), two photosensitive COFs, namely TFPA-TAPT-COF-Q and TFPA-TPB-COF-Q, are successfully constructed. The obtained quinoline-linked COFs display improved stability and photocatalytic activity, making them suitable photocatalysts for photocatalytic reactions under harsh conditions, as verified by the recyclable photocatalytic reactions of organic acid involving oxidative decarboxylation and organic base involving benzylamine coupling. Under strong oxidative condition, the quinoline-linked COFs show a high efficiency up to 11831.6 µmol·g-1·h-1 and a long-term recyclable usability for photocatalytic production of H2O2, while the pristine imine-linked COFs are less catalytically active and easily decomposed in these harsh conditions. The results demonstrate that enhancing the linkage robustness of photoactive COFs is a promising strategy to construct heterogeneous catalysts for photocatalytic reactions under harsh conditions.

Efficient Acidic Photoelectrochemical Water Splitting Enabled by Ru Single Atoms Anchored on Hematite Photoanodes.

Photoelectrochemical (PEC) water splitting in acidic media holds promise as an efficient approach to renewable hydrogen production. However, the development of highly active and stable photoanodes under acidic conditions remains a significant challenge. Herein, we demonstrate the remarkable water oxidation performance of Ru single atom decorated hematite (Fe2O3) photoanodes, resulting in a high photocurrent of 1.42 mA cm-2 at 1.23 VRHE under acidic conditions. Comprehensive experimental and theoretical investigations shed light on the mechanisms underlying the superior activity of the Ru-decorated photoanode. The presence of single Ru atoms enhances the separation and transfer of photogenerated carriers, facilitating efficient water oxidation kinetics on the Fe2O3 surface. This is achieved by creating additional energy levels within the Fe2O3 bandgap and optimizing the free adsorption energy of intermediates. These modifications effectively lower the energy barrier of the rate-determining step for water splitting, thereby promoting efficient PEC hydrogen production.

Accelerating Sulfur Redox Kinetics by Electronic Modulation and Drifting Effects of Pre-Lithiation Electrocatalysts.

Efficient catalyst design is crucial for addressing the sluggish multi-step sulfur redox reaction (SRR) in lithium-sulfur batteries (LiSBs), which are among the promising candidates for the next-generation high-energy-density storage systems. However, the limited understanding of the underlying catalytic kinetic mechanisms and the lack of precise control over catalyst structures pose challenges in designing highly efficient catalysts, which hinder the LiSBs' practical application. Here, drawing inspiration from the theoretical calculations, the concept of precisely controlled pre-lithiation SRR electrocatalysts is proposed. The dual roles of channel and surface lithium in pre-lithiated 1T'-MoS2 are revealed, referred to as the "electronic modulation effect" and "drifting effect", respectively, both of which contribute to accelerating the SRR kinetics. As a result, the thus-designed 1T'-Lix MoS2 /CS cathode obtained by epitaxial growth of pre-lithiated 1T'-MoS2 on cubic Co9 S8 exhibits impressive performance with a high initial specific capacity of 1049.8 mAh g-1 , excellent rate-capability, and remarkable long-term cycling stability with a decay rate of only 0.019% per cycle over 1000 cycles at 3 C. This work highlights the importance of precise control in pre-lithiation parameters and the synergistic effects of channel and surface lithium, providing new valuable insights into the design and optimization of SRR electrocatalysts for high-performance LiSBs.

Laser Synthesis of PtMo Single-Atom Alloy Electrode for Ultralow Voltage Hydrogen Generation.

Maximizing atom-utilization efficiency and high current stability are crucial for the platinum (Pt)-based electrocatalysts for hydrogen evolution reaction (HER). Herein, the Pt single-atom anchored molybdenum (Mo) foil (Pt-SA/Mo-L) as a single-atom alloy electrode is synthesized by the laser ablation strategy. The local thermal effect with fast rising-cooling rate of laser can achieve the single-atom distribution of the precious metals (e.g., Pt, Rh, Ir, and Ru) onto the Mo foil. The synthesized self-standing Pt-SA/Mo-L electrode exhibits splendid catalytic activity (31 mV at 10 mA cm-2 ) and high-current-density stability (≈850 mA cm-2 for 50 h) for HER in acidic media. The strong coordination of Pt-Mo bonding in Pt-SA/Mo-L is critical for the efficient and stable HER. In addition, the ultralow electrolytic voltage of 0.598 V to afford the current density of 50 mA cm-2 is realized by utilization of the anodic molybdenum oxidation instead of the oxygen evolution reaction (OER). Here a universal synthetic strategy of single-atom alloys (PtMo, RhMo, IrMo, and RuMo) as self-standing electrodes is provided for ultralow voltage and membrane-free hydrogen production.

Lattice-mismatch-free construction of III-V/chalcogenide core-shell heterostructure nanowires.

Growing high-quality core-shell heterostructure nanowires is still challenging due to the lattice mismatch issue at the radial interface. Herein, a versatile strategy is exploited for the lattice-mismatch-free construction of III-V/chalcogenide core-shell heterostructure nanowires by simply utilizing the surfactant and amorphous natures of chalcogenide semiconductors. Specifically, a variety of III-V/chalcogenide core-shell heterostructure nanowires are successfully constructed with controlled shell thicknesses, compositions, and smooth surfaces. Due to the conformal properties of obtained heterostructure nanowires, the wavelength-dependent bi-directional photoresponse and visible light-assisted infrared photodetection are realized in the type-I GaSb/GeS core-shell heterostructure nanowires. Also, the enhanced infrared photodetection is found in the type-II InGaAs/GeS core-shell heterostructure nanowires compared with the pristine InGaAs nanowires, in which both responsivity and detectivity are improved by more than 2 orders of magnitude. Evidently, this work paves the way for the lattice-mismatch-free construction of core-shell heterostructure nanowires by chemical vapor deposition for next-generation high-performance nanowire optoelectronics.

An Amorphous Native Oxide Shell for High Bias-Stress Stability Nanowire Synaptic Transistor.

The inhomogeneous native oxide shells on the surfaces of III-V group semiconductors typically yield inferior and unstable electrical properties metrics, challenging the development of next-generation integrated circuits. Herein, the native GaOx shells are profitably utilized by a simple in-situ thermal annealing process to achieve high-performance GaSb nanowires (NWs) field-effect-transistors (FETs) with excellent bias-stress stability and synaptic behaviors. By an optimal annealing time of 5 min, the as-constructed GaSb NW FET demonstrates excellent stability with a minimal shift of transfer curve (ΔVth ≈ 0.54 V) under a 60 min gate bias, which is far more stable than that of pristine GaSb NW FET (ΔVth ≈ 8.2 V). When the high bias-stress stability NW FET is used as the chargeable-dielectric free synaptic transistor, the typical synaptic behaviors, such as short-term plasticity, long-term plasticity, spike-time-dependent plasticity, and reliable learning stability are demonstrated successfully through the voltage tests. The mobile oxygen ion in the native GaOx shell strongly offsets the trapping states and leads to enhanced bias-stress stability and charge retention capability for synaptic behaviors. This work provides a new way of utilizing the native oxide shell to realize stable FET for chargeable-dielectric free neuromorphic computing systems.

Chiral Superlattices Self-Assembled from Post-Modified Metal-Organic Polyhedra.

Metal-organic polyhedra (MOPs) are inherently porous, discrete, and solvent-dispersive, and directing them into chiral superlattices through direct self-assembly remains a considerable challenge due to their nanoscale size and structural complexity. In this work, we illustrate a postmodification protocol to covalently conjugate a chiral cholesteryl pendant to MOPs. Postmodification retained the coordination cores and allowed for reaction-induced self-assembly in loosely packed nanosized columns without supramolecular chirality. Solvent-processed bottom-up self-assembly in aqueous media facilitated the well-defined packing into twisted superlattices with a 5 nm lattice parameter. Experimental and computational results validated the role of intercholesteryl forces in spinning the nanosized MOPs, which achieved the chirality transfer to supramolecular scale with chiral optics. This work establishes a novel protocol in rational design of MOP-based chiroptical materials for potential applications of enantioselective adsorption, catalysis, and separation.

Pulsed-Laser-Triggered Piezoelectric Photocatalytic CO2 Reduction over Tetragonal BaTiO3 Nanocubes.

The recombination of photoinduced carriers in photocatalysts is considered one of the biggest barriers to the increase of photocatalytic efficiency. Piezoelectric photocatalysts open a new route to realize rapid carrier separation by mechanically distorting the lattice of piezoelectric nanocrystals to form a piezoelectric potential within the nanocrystals, generally requiring external force (e.g., ultrasonic radiation, mechanical stirring, and ball milling). In this study, a low-power UV pulsed laser (PL) (3 W, 355 nm) as a UV light source can trigger piezoelectric photocatalytic CO2 reduction of tetragonal BaTiO3 (BTO-T) in the absence of an applied force. The tremendous transient light pressure (5.7 × 107  Pa, 2.7 W) of 355 nm PL not only bends the energy band of BTO-T, thus allowing reactions that cannot theoretically occur to take place, but also induces a pulsed built-in electric field to determine an efficient photoinduced carrier separation. On that basis, the PL-triggered piezoelectric photocatalytic CO2 reduction realizes the highest reported performance, reaching a millimole level CO yield of 52.9 mmol g-1 h-1 and achieving efficient photocatalytic CO2 reduction in the continuous catalytic system. The method in this study is promising to contribute to the design of efficient piezoelectric photocatalytic reactions.

Electron-rich Au nanocrystals/Co3O4 interface for enhanced electrochemical nitrate reduction into ammonia.

Solar-driven electrochemical NO3- reduction reaction (NO3-RR) is a clean and sustainable strategy that can convert pollutant NO3- in wastewater to value-added NH3. In recent years, cobalt oxides-based catalysts have shown their intrinsic catalytic properties toward NO3-RR but still have room for improvement through catalyst design. Coupling metal oxides with noble metal has been demonstrated to improve electrochemical catalytic efficiency. Here, we use Au species to tune the surface structure of Co3O4 and improve the efficiency of NO3-RR to NH3. The obtained Au nanocrystals-Co3O4 catalyst exhibited an onset potential of 0.54 V vs RHE, NH3 yield rate of 27.86 µg/h·cm2, and Faradaic efficiency (FE) of 83.1% at 0.437 V vs RHE in an H-cell, which is much higher than Au small species (Au clusters or single atoms)-Co3O4 (15.12 µg/h·cm2) and pure Co3O4 (11.38 µg/h·cm2), respectively. Combined experiments with theory calculations, we attributed the enhanced performance of Au nanocrystals-Co3O4 to the reduced energy barrier of *NO hydrogenation to the *NHO and suppression of HER, which originated from the charge transfer from Au to Co3O4. Using an amorphous silicon triple-junction (a-Si TJ) as the solar cell and an anion exchange membrane electrolyzer (AME), an unassisted solar-driven NO3-RR to NH3 prototype was realized with a yield rate of 4.65 mg/h and FE of 92.1%.

A Bioinspired Atomically Thin Nanodot Supported Single-Atom Nanozyme for Antibacterial Textile Coating.

Surface antibacterial coatings with outstanding antibacterial efficiency have attracted increasing attention in medical protective clothing and cotton surgical clothing. Although nanozymes, as a new generation of antibiotics, are used to combat bacteria, their catalytic performance remains far from satisfactory as alternatives to natural enzymes. Single-atom nanodots provide a solution to the low catalytic activity bottleneck of nanozymes. Here, atomically thin C3 N4 nanodots supported single Cu atom nanozymes (Cu-CNNDs) are developed by a self-tailoring approach, which exhibits catalytic efficiency of 8.09 × 105 M-1 s-1 , similar to that of natural enzyme. Experimental and theoretical calculations show that excellent peroxidase-like activity stems from the size effect of carrier optimizing the coordination structure, leading to full exposure of Cu-N3 active site, which improves the ability of H2 O2 to generate hydroxyl radicals (•OH). Notably, Cu-CNNDs exhibit over 99% superior antibacterial efficacy and are successfully grafted onto cotton fabrics. Thus, Cu-CNNDs blaze an avenue for exquisite biomimetic nanozyme design and have great potential applications in antibacterial textiles.

Two triplet emitting states in one emitter: Near-infrared dual-phosphorescent Au20 nanocluster.

Intrinsic dual-emission (DE) of gold nanoclusters in the near-infrared (NIR) are fascinating for fundamental importance and practical applications, but their synthesis remains a formidable challenge and sophisticated excited-state processes make elucidating DE mechanisms much more arduous. Here, we report an all-alkynyl-protected gold nanocluster, Au20, showing a prolate Au12 tri-octahedral kernel surrounded by two Au2(CZ-PrA)3 dimers, four Au(CZ-PrA)2 monomers, and two CZ-PrA- bridges. Au20 exhibits distinguished photophysical properties including NIR DE at 820 and 940 nm, microsecond radiative relaxation, and 6.26% photoluminescent quantum yield at ambient environment in nondegassed solution. Combining systematic studies on steady/transient spectroscopy and theoretical calculation, we identified two triplet charge transfer (CT) states, ligand-to-kernel and kernel-based CT states as DE origins. Furthermore, this NIR DE exhibits highly independent and sensitive response to surrounding environments, which well coincide with its mechanism. This work not only provides a substantial structure model to understand a distinctive DE mechanism but also motivates the further development of NIR DE materials.

New Approach to Low-Power-Consumption, High-Performance Photodetectors Enabled by Nanowire Source-Gated Transistors.

Power consumption makes next-generation large-scale photodetection challenging. In this work, the source-gated transistor (SGT) is adopted first as a photodetector, demonstrating the expected low power consumption and high photodetection performance. The SGT is constructed by the functional sulfur-rich shelled GeS nanowire (NW) and low-function metal, displaying a low saturated voltage of 0.61 V ± 0.29 V and an extremely low power consumption of 7.06 pW. When the as-constructed NW SGT is used as a photodetector, the maximum value of the power consumption is as low as 11.96 nW, which is far below that of the reported phototransistors working in the saturated region. Furthermore, benefiting from the adopted SGT device, the photodetector shows a high photovoltage of 6.6 × 10-1 V, a responsivity of 7.86 × 1012 V W-1, and a detectivity of 5.87 × 1013 Jones. Obviously, the low power consumption and excellent responsivity and detectivity enabled by NW SGT promise a new approach to next-generation, high-performance photodetection technology.

Low-Coordination Single Au Atoms on Ultrathin ZnIn2 S4 Nanosheets for Selective Photocatalytic CO2 Reduction towards CH4.

Selective CO2 photoreduction to hydrocarbon fuels such as CH4 is promising and sustainable for carbon-neutral future. However, lack of proper binding strengths with reaction intermediates makes it still a challenge for photocatalytic CO2 methanation with both high activity and selectivity. Here, low-coordination single Au atoms (Au1 -S2 ) on ultrathin ZnIn2 S4 nanosheets was synthesized by a complex-exchange route, enabling exceptional photocatalytic CO2 reduction performance. Under visible light irradiation, Au1 /ZnIn2 S4 catalyst exhibits a CH4 yield of 275 µmol g-1 h-1 with a selectivity as high as 77 %. As revealed by detailed characterizations and density functional theory calculations, Au1 /ZnIn2 S4 with Au1 -S2 structure not only display fast carrier transfer to underpin its superior activity, but also greatly reduce the energy barrier for protonation of *CO and stabilize the *CH3 intermediate, thereby leading to the selective CH4 generation from CO2 photoreduction.

Carrier Separation Enhanced by High Angle Twist Grain Boundaries in Cesium Lead Bromide Perovskites.

Grain boundaries (GBs) have a profound impact on mechanical, chemical, and physical properties of polycrystalline materials. Comprehension of atomic and electronic structures of different GBs in materials can help to understand their impact on materials' properties. Here, with aberration-corrected scanning transmission electron microscopy (STEM), the atomic structure of a 90° twist GB s in CsPbBr3 is determined, and its impact on electron-hole pair separation is predicted. The 90° twist GB has a coherent interface and the same chemical composition as the bulk except for the lattice twist. Density functional theory (DFT) calculation results indicate that the twist GB has an electronic structure similar to that of the bulk CsPbBr3. An electronic potential at the GBs enhances the separation of photogenerated carriers and promotes the motion of electrons across the GBs. These results extend the understanding of atomic and electronic structure of GBs in halide perovskites and propose a potential strategy to eliminate the influence of GBs by GB engineering.