Oxygen Vacancy-Enhanced Ni3N-CeO2/NF Nanoparticle Catalysts for Efficient and Stable Electrolytic Water Splitting.

Highly efficient and cost-effective electrocatalysts are of critical significance in the domain of water electrolysis. In this study, a Ni3N-CeO2/NF heterostructure is synthesized through a facile hydrothermal technique followed by a subsequent nitridation process. This catalyst is endowed with an abundance of oxygen vacancies, thereby conferring a richer array of active sites. Therefore, the catalyst demonstrates a markedly low overpotential of 350 mV for the Oxygen Evolution Reaction (OER) at 50 mA cm-2 and a low overpotential of 42 mV for the Hydrogen Evolution Reaction (HER) at 10 mA cm-2. Serving as a dual-function electrode, this electrocatalyst is employed in overall water splitting in alkaline environments, demonstrating impressive efficiency at a cell voltage of 1.52 V of 10 mA cm-2. The in situ Raman spectroscopic analysis demonstrates that cerium dioxide (CeO2) facilitates the rapid reconfiguration of oxygen vacancy-enriched nickel oxyhydroxide (NiOOH), thereby enhancing the OER performance. This investigation elucidates the catalytic role of CeO2 in augmenting the OER efficiency of nickel nitride (Ni3N) for water electrolysis, offering valuable insights for the design of high-performance bifunctional catalysts tailored for water splitting applications.

Oxygen Vacancy and Heterostructure Modulation of Co2P/Fe2P Electrocatalysts for Improving Total Water Splitting.

Designing a stable and highly active catalyst for hydrogen evolution and oxygen evolution reactions (HER/OER) is essential for the industrialization of hydrogen energy but remains a major challenge. This work reports a simple approach to fabricating coupled Co2P/Fe2P nanorod array catalyst for overall water decomposition, demonstrating the source of excellent activity in the catalytic process. Under alkaline conditions, Co2P/Fe2P heterostructures exhibit an overpotential of 96 and 220 mV for HER and OER, respectively, at 10 mA cm-2. For total water splitting, a low voltage of 1.56 V is required to provide a current density of 10 mA cm-2. And the catalyst exhibits long-term durability for 30 h at a high current density of 250 mA cm-2. The analysis of the results revealed that the presence of interfacial oxygen vacancies and the strong interaction between Co2P/Fe2P provided the catalyst with more electrochemically active sites and a faster charge transfer capability, which improved the hydrolysis dissociation process. Electrochemically active metal (oxygen) hydroxide phases were produced after OER stability testing. The results of this study prove its great potential in practical industrial electrolysis and provide a reasonable and feasible strategy for the design of nonprecious metal phosphide electrocatalysts.

Effect of pyrolysis temperature on the binding characteristics of DOM derived from livestock manure biochar with Cu(II).

Biochar-derived dissolved organic matter (BDOM) has the potential to influence the environmental application of biochar and the behavior of heavy metals. In this study, the binding properties of BDOM derived from livestock manure biochar at different pyrolysis temperatures with Cu(II) were investigated based on a multi-analytical approach. The results showed that the DOC concentration, aromatics, and humification degree of BDOM were higher in the process of low pyrolysis of biochar. The pyrolysis temperature changed the composition of BDOM functional groups, which affected the binding mechanism of BDOM-Cu(II). Briefly, humic-like and protein-like substances dominated BDOM-Cu(II) binding at low and high pyrolysis temperatures, respectively. The higher binding capacity for Cu(II) was exhibited by BDOM derived from the lower pyrolysis temperature, due to the carboxyl as the main binding site in humic acid had high content and binding ability at low-temperature. The amide in proteins only participated in the BDOM-Cu(II) binding at high pyrolysis temperature, and polysaccharides also played an important role in the binding process. Moreover, the biochar underwent the secondary reaction at certain high temperatures, which led to condensation reaction of the aromatic structure and the conversion of large molecules into small molecules, affecting the BDOM-Cu(II) binding sites.

Sulfonyl Molecules Induced Oriented Lithium Deposition for Long-Term Lithium Metal Batteries.

Dendrites growth and unstable interfacial Li+ transport hinder the practical application of lithium metal batteries (LMBs). Herein, we report an active layer of 2,4,6-trihydroxy benzene sulfonyl fluorine on copper substrate that induces oriented Li+ deposition and generates highly crystalline solid-electrolyte interphase (SEI) to achieve high-performance LMBs. The lithiophilic -SO2 - groups of highly crystalline SEI accept the rapidly transported Li+ ions and form a dense inner layer of LiF and Li3 N, which regulate Li+ plating morphology along the (110) crystal surface toward dendrite-free Li anode. Thus, Li||Cu cells with lithiophilic SEI achieve an average deposition efficiency of 99.8 % after 700 cycles, and Li||Li cells operate well for 1100 h. Besides, Li||LiNi0.8 Co0.1 Mn0.1 O2 cells with modified SEI exhibit a capacity retention that is 14 times than that of conventional SEI. Even at -60 °C, Li||Cu cells reach stable deposition efficiency of 83.2 % after 100 cycles.

Silver Nanowires Cascaded Layered Double Hydroxides Nanocages with Enhanced Directional Electron Transport for Efficient Electrocatalytic Oxygen Evolution.

Designing and fabricating highly efficient oxygen evolution reaction (OER) electrocatalytic materials for water splitting is a promising and practical approach to green and sustainable low-carbon energy systems. Herein, a facile in situ growth self-template strategy by using ZIF-67 as a consumable layered double hydroxides (LDHs) template and silver nanowires (AgNWs) as 1D conductive cascaded substrate to controllably synthesize the target AgNWs@CoFe-LDH composites with unique hollow shell sugar gourd-like structure and enhanced directional electron transport effect is reported. The AgNWs exhibit the key functions of the close connection of CoFe-LDH nanocages and the support of the directional electron transport effect in the composite catalyst inducing electrons directionally moving from CoFe-LDH to AgNWs. Meanwhile, the CoFe-LDH nanocages with ultrathin nanosheets and hollow structural properties show abundant active sites for electrocatalytic oxygen generation. The versatile AgNWs@CoFe-LDH catalyst with optimized components, enhanced directional electron transport, and synergistic effect achieves high OER performance with the overpotential of 207 mV and long-term 50 h stability at 10 mA cm-2 in an alkaline medium. Moreover, in-depth insights into the microstructure, structure-activity relationships, identification of key intermediate species, and a proton-coupled four-electron OER mechanism based on experimental discovery and theoretical calculation are also demonstrated.

Research Progress on the Composite Methods of Composite Electrolytes for Solid-State Lithium Batteries.

In the current challenging energy storage and conversion landscape, solid-state lithium metal batteries with high energy conversion efficiency, high energy density, and high safety stand out. Due to the limitations of material properties, it is difficult to achieve the ideal requirements of solid electrolytes with a single-phase electrolyte. A composite solid electrolyte is composed of two or more different materials. Composite electrolytes can simultaneously offer the advantages of multiple materials. Through different composite methods, the merits of various materials can be incorporated into the most essential part of the battery in a specific form. Currently, more and more researchers are focusing on composite methods for combining components in composite electrolytes. The ion transport capacity, interface stability, machinability, and safety of electrolytes can be significantly improved by selecting appropriate composite methods. This review summarizes the composite methods used for the components of composite electrolytes, such as filler blending, embedded framework, and multilayer bonding. It also discusses the future development trends of all-solid-state lithium batteries (ASSLBs).

High-performance bismuth vanadate photoanodes cocatalyzed with nitrogen, sulphur co-doped ferrocobalt-metal organic frameworks thin layer for photoelectrochemical water splitting.

In this study, we prepare a highly efficient BiVO4 photoanode co-catalyzed with an ultrathin layer of N, S co-doped FeCo-Metal Organic Frameworks (MOFs) for photoelectrochemical water splitting. The introduction of N and S into FeCo-MOFs enhances electron and mass transfer, exposing more catalytic active sites and significantly improving the catalytic performance of N, S co-doped FeCo-based MOFs in water oxidation. The optimized BiVO4/NS-FeCo-MOFs photoanode exhibits impressive results, with a photocurrent density of 5.23 mA cm-2 at 1.23 V vs. Reversible Hydrogen Electrode (RHE) and an incident photon-to-charge conversion efficiency (IPCE) of 74.4 % at 450 nm in a 0.1 M phosphate buffered solution (pH = 7). These values are 4.84 times and 6.2 times higher than those of the original BiVO4 photoanode, respectively. Furthermore, the optimized BiVO4/NS-FeCo-MOFs photoanode demonstrates exceptional long-term stability, maintaining 96 % of the initial current after five hours.

Kinetics Conditioning of (Electro) Chemically Stable Zn Anode with pH Regulation Toward Long-Life Zn-Storage Devices.

The safety, low cost, and high power density of aqueous Zn-based devices (AZDs) appeal to large-scale energy storage. Yet, the presence of hydrogen evolution reaction (HER) and chemical corrosion in the AZDs leads to local OH- concentration increasement and the formation of ZnxSOy(OH)z•nH2O (ZHS) by-products at the Zn/electrolyte interface, causing instability and irreversibility of the Zn-anodes. Here, a strategy is proposed to regulate OH- by introducing a bio-sourced/renewable polypeptide (ɛ-PL) as a pH regulator in electrolyte. The consumption of OH- species is evaluated through in vitro titration and cell in vivo in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy at a macroscopic and molecular level. The introduction of ɛ-PL is found to significantly suppress the formation of ZHS and associated side reactions, and reduce the local coordinated H2O of the Zn2+ solvation shell, widening electrochemical stable window and suppressing OH- generation during HER. As a result, the inclusion of ɛ-PL improves the cycle time of Zn/Zn symmetrical cells from 15 to 225 h and enhances the cycle time of aqueous Zn- I2 cells to 1650 h compared to those with pristine electrolytes. This work highlights the potential of kinetical OH- regulation for by-product and dendrite-free AZDs.

Bio-inspired Ti3C2Tx MXene composite coating for enhancing corrosion resistance of aluminum alloy in acidic environments.

Aluminum alloy (Al alloy) suffers from severe corrosion in acidic solution. Two-dimensional (2D) MXene-based composite coatings show great prospects for corrosion protection on metals used in special conditions. The composite coatings still face challenges in complex functionalization and orientation control. In harsh conditions, the long-term ability and roles of MXene in corrosion protection are still not clear. Here, a bio-inspired myristic-calcium chloride-Ti3C2Tx MXene (MA + CaCl2 + MXene) composite coating is successfully prepared on aluminum alloy (Al alloy) by electrodeposition process. Electrochemical tests, surface morphology, and chemical composition are analyzed to investigate the corrosion resistance and protection mechanism of the MXene coating in acidic solution (0.5 M H2SO4 + 2 ppm HF). As a result, the incorporation of MXene can significantly reduce corrosion current density (7.498 × 10-8 A/cm2) by âˆ¼ 5 orders of magnitude and impedance modulus at 0.01 Hz (|Z|0.01 Hz) value of the composite coating is 196.8 Ω·cm2, which is over 4 times higher than that of bare Al alloy (40.74 Ω·cm2) after immersion test for 72 h. Furthermore, the in-situ corrosion test confirms the enhanced corrosion resistance of the MA + CaCl2 + MXene composite coating. The MXene can increase coating thickness to 23.6 ± 0.4 µm, reduce porosity to (5.845 ± 1) × 10-5, decrease the diffusion coefficients of H+ to (1.587 ± 0.3) × 10-9 cm2/s, and enhance the adhesion of the coating to the substrate (the delamination time exceeds 5 h), thus providing improved anti-corrosion ability. This strategy opens up new prospects for construction of 2D MXene-based anti-corrosion coatings.

Electrodeposition-Assisted Crystal Growth Regulation of PdBi Clusters on Carbon Cloths for Ethanol Oxidation.

Carbon-supported Pd-based clusters are one of the most promising anodic catalysts for ethanol oxidation reaction (EOR) due to their encouraging activity and practical applications. However, unclear growth mechanism of Pd-based clusters on the carbon-based materials has hindered their extensive applications. Herein, we first introduce multi-void spherical PdBi cluster/carbon cloth (PdBi/CC) composites by an electrodeposition routine. The growth mechanism of PdBi clusters on the CC supports has been systemically investigated by evaluating the selected samples and tuning their compositions, which involve the big difference in standard redox potential between Pd2+/Pd and Bi3+/Bi and easy adsorption of Bi3+ on the surface of Pd-rich seeds. Benefitting from the ensembles of many nanocrystal subunits, multi-void spherical PdBi clusters can present collective properties and novel functionalities. In addition, the outstanding characteristics of CC supports enable PdBi clusters with stable nanostructures. Thanks to the unique structure, Pd20Bi/CC catalysts manifest higher EOR activity and better stability compared to Pd/CC. Systematic characterizations and a series of CO poisoning tests further confirm that the dramatically enhanced EOR activity and stability can be attributed to the incorporation of Bi species and the strong coupling of the structure between PdBi clusters and CC supports.

WOx nanoparticles coupled with nitrogen-doped porous carbon toward electrocatalytic N2 reduction.

The electrocatalytic nitrogen reduction reaction (eNRR) is a sustainable and green alternative to the traditional Haber-Bosch process. However, the chemical inertness of nitrogen gas and the competitive hydrogen evolution reaction significantly limit the catalytic performance of eNRR. Although tungsten oxide-based eNRR catalysts could donate unpaired electrons to the antibonding orbitals of N2 and accept lone electron pairs from N2 to dissociate NN triple bonds, the low electrical conductivity and the influence of the variable valence of W still affect the catalytic activity. Herein, a high-performance eNRR catalyst WOx nanoparticle/nitrogen-doped porous carbon (WOx/NPC) was prepared by a one-step thermal pyrolysis method. The results reveal that WOx gradually changes from the dominant WO2 phase to the WO3 phase. WOx/NPC-700 °C with WO2 NPs anchored on the surfaces of NPC via W-N bonding could deliver a high NH3 yield of 46.8 µg h-1 mg-1 and a high faradaic efficiency (FE) of 10.2%. The edge W atomic site on WOx/NPC is demonstrated to be the active center which could activate a stable NN triple bond with an electron-donating ability. Benefiting from the covalent interaction between the WOx nanoparticles and NPC, WOx/NPC also shows high electrocatalytic stability.

Li3Bi/Li2O layer with uniform built-in electric field distribution for dendrite free lithium metal batteries.

Lithium metal batteries have garnered significant attention as a promising energy storage technology, offering high energy density and potential applications across various industries. However, the formation of lithium dendrites during battery cycling poses a considerable challenge, leading to performance degradation and safety hazards. This study aims to address this issue by investigating the effectiveness of a protective layer on the lithium metal surface in inhibiting dendrite growth. The hypothesis is that continuous lithium consumption during battery cycling is a primary contributor to dendrite formation. To test this hypothesis, a protective layer of Li3Bi/Li2O was applied to the lithium foil through immersion in a BiN3O9 solution. Experimental techniques including kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations were employed to analyze the structural and electronic properties of the Li3Bi/Li2O layer. The findings demonstrate successful doping of Bi into the Li coating, forming Bi-Bi and Bi-O bonds. KPFM measurements reveal a higher work function of Li3Bi/Li2O, indicating its potential as an effective protective layer. DFT calculations further support this observation by revealing a greater adsorption energy of lithium on the Li3Bi/Li2O layer compared to the bulk material. Charge density analysis suggests that the adsorption of Li atoms onto the Li3Bi/Li2O layer induces a redistribution of charge, resulting in increased electron availability on the surface and preventing electrode-electrolyte contact. This study provides insights into the role of the Li3Bi/Li2O protective layer in inhibiting dendrite growth in lithium metal batteries. By mitigating dendrite formation, the protective layer holds promise for enhancing battery performance and longevity. These findings contribute to the development of strategies for improving the stability and reliability of lithium metal batteries, facilitating their wider adoption in energy storage applications.

Nano-semiconductor material stabilized Zn metal anode for long-life aqueous Zn-ion batteries.

The advantages of aqueous Zn-ion batteries lie in the affordability and environmental friendliness. Nonetheless, the use of aqueous Zn-ion batteries is severely hindered by key issues such dendrite formation and side reactions in Zn metal anodes. It is able to works well so as to create a stable interface layer, which controls the development of dendrites and adverse reactions. In this study, it is recommended that the coating formed by nano-semiconductor material graphitic carbon nitride (g-C3N4) should be applied to the surface of Zn metal to evenly disperse the electric field, as well as inhibit the development of tip effect, thus preventing Zn dendrite growth. Zn deposition occurs quickly and steadily as a result of Zn2+ ions being adsorbed and the Zn2+ ion flow being reallocated by the zincophilicity of N atoms in the coating. The Zn symmetrical battery can be stable cycled for 1,000 h at a current density of 0.5 mA cm-2, with its overall areal capacity of 0.5mAh cm-2, which is attributed to these benefits of the coating. It can be stable circulated for 500 h at a high current density of 5 mA cm-2, with its total areal capacity of 1mAh cm-2. The completely constructed Zn-g-C3N4//V2O5 according exhibits exceptional long-termcycle stability. Under the current density of 2 A/g, the initial capacity is 312.3 mAh g-1, which can cycle be stable circulated for 1,000 cycles.Under the high current density of 5 A/g, the whole battery's capacity keeping holdingrate is 70% after 2000 cycles, and the coulomb efficiency (CE) is extremely near to 100%.

Flower ball cathode assembled from Cu doped Co3S4/Ni3S2 ultrathin nanosheets in a photocatalytic fuel cell for efficient photoelectrochemical rifampicin purification and simultaneous electricity generation based on a CuO QDs/TiO2/WO3 photoanode.

Herein, an efficient CuO QDs/TiO2/WO3 photoanode and a Cu doped Co3S4/Ni3S2 cathode were successfully synthesized. The optimized CuO QDs/TiO2/WO3 photoanode achieved a photocurrent density of 1.93 mA cm-2 at 1.23 vs. RHE, which was 2.27 times that of a WO3 photoanode. The CuO QDs/TiO2/WO3-buried junction silicon (BJS) photoanode was coupled with the Cu doped Co3S4/Ni3S2 cathode to construct a novel photocatalytic fuel cell (PFC) system. The as-established PFC system showed a high rifampicin (RFP) removal ratio of 93.4% after 90 min and maximum power output of 0.50 mW cm-2. Quenching tests and EPR spectra demonstrated that ˙OH, ˙O2- and 1O2 were the main reactive oxygen species in the system. This work provides a possibility to construct a more efficient PFC system for environmental protection and energy recovery in the future.

Anomalous Inferior Zn Anode in High-Concentration Electrolyte: Leveraging Solid-Electrolyte-Interface for Stabilized Cycling of Aqueous Zn-Metal Batteries.

Aqueous Zn-metal batteries (AZMBs) are promising large-scale energy storage devices for their high safety and theoretical capacity. However, unstable Zn-electrolyte interface and severe side reactions have excluded AZMBs from long cycling required by practically reversible energy storage. Traditional high-concentration electrolyte is an effective strategy to suppress dendrites growth and resolve the poor electrochemical stability and reversibility of Zn-metal anodes, yet how scientifically universal such strategy is for hybrid electrolyte of different concentrations remains unclear. Herein, we studied the electrochemical behaviors of AZMBs comprising a ZnCl2 -based DMSO/H2 O electrolyte of two distinct concentrations (1 m vs. 7 m). The electrochemical stability/reversibility of Zn anodes in both symmetric and asymmetric cells with high-concentration electrolytes are unusually inferior to the ones with low-concentration electrolyte. It was found that more DMSO components in the solvation sheath of low-concentration electrolyte exist at the Zn-electrolyte interface than in high-concentration counterpart, enabling higher organic compositions in solid-electrolyte-interface (SEI). The rigid inorganic and flexible organic compositions of SEI decomposed from the low-concentration electrolyte is accounted for improved cycling and reversibility of Zn metal anodes and the respective batteries. This work reveals the critical role of SEI than the high concentration itself in delivering stable electrochemical cycling in AZMBs.

Photo-Cross-Linked Polymeric Dispersants of Comb-Shaped Benzophenone-Containing Poly(ether amine).

Efficient dispersion of nanoparticles (NPs) is a crucial challenge in the preparation and application of composites that contain NPs, particularly in coatings, inks, and related materials. Physical adsorption and chemical modification are the two common methods used to disperse NPs. However, the former suffers from desorption, and the latter is more specific and has limited versatility. To address these issues, we developed a novel photo-cross-linked polymeric dispersant, comb-shaped benzophenone-containing poly(ether amine) (bPEA), using a one-pot nucleophilic/cyclic-opening addition reaction. The results demonstrated that the bPEA dispersant forms a dense and stable shell on the surface of pigment NPs through physical adsorption and subsequent chemical photo-cross-linking, which effectively overcome the drawbacks of the desorption occurred in physical adsorption and the specificity of the chemical modification. By means of the dispersing effect of bPEA, the obtained pigment dispersions show high solvent, thermal, and pH stability without flocculation during storage. Moreover, the NPs dispersants show good compatibility with screen printing, coating, and 3D printing, endowing the ornamental products with high uniformity, color fastness, and less color shading. These properties make bPEA dispersants ideal candidates in fabrication dispersions of other NPs.

Curved Porous PdCu Metallene as a High-Efficiency Bifunctional Electrocatalyst for Oxygen Reduction and Formic Acid Oxidation.

Designing high-efficiency and newly developed Pd-based bifunctional catalytic materials still faces tremendous challenges for oxygen reduction reaction (ORR) and formic acid oxidation reaction (FAO). Metallene materials with unique structural features are considered strong candidates for enhancing the catalytic performance. In this work, we synthesized copper-doped two-dimensional curved porous Pd metallene nanomaterials via a simplistic one-pot solvothermal method. The updated catalysts served as sturdy bifunctional electrocatalysts for cathodal ORR and anodic FAO. In particular, the developed PdCu metallene exhibits excellent half-wave potential (0.943 V vs RHE) and mass activity (MA) (1.227 A mgPt-1) in alkaline solutions, which are 1.09 and 6.26 times higher than those of commercial Pt/C, respectively, indicating that the nanomaterials have abundant active sites, displaying surpassing catalytic performance for oxygen reduction. Furthermore, in an acidic formic acid electrolyte, PdCu metallene exhibits prominent MA with a value of 0.905 A mgPd-1, which is 2.76 times that of commercial Pd/C. The remarkable bifunctional catalytic performance of metallene materials can be attributed to the special structure and electronic effects. This work shows that metallene materials with curved and porous properties provide a scientific idea for the development and design of efficient and steady electrocatalysts.

Correlating Oxidation State and Surface Ligand Motifs with the Selectivity of CO2 Photoreduction to C2 Products.

The design for non-Cu-based catalysts with the function of producing C2+ products requires systematic knowledge of the intrinsic connection between the surface state as well as the catalytic activity and selectivity. In this work, photochemical in situ spectral surface characterization techniques combined with the first principle calculations (DFT) were applied to investigate the relationships between the composition of surface states, coordinated motifs, and catalytic selectivity of a titanium oxynitride catalyst. When the catalyst mediates CO2 photoreduction, C2 product selectivity is positively correlated with the surface Ti2+ /Ti3+ ratio and the surface oxidation state is regulated and controlled by coordinated motifs of N-Ti-O/V[O], which can reduce the potential dimerization energy barriers of *CO-CO* and promote spontaneous formation of the subsequent *CO-CH2 * intermediate. This phenomenon provides a new perspective for the design of heterogeneous catalysts for photoreduction of CO2 into useful products.

Repurposing of spent lithium-ion battery separator as a green reductant for efficiently refining the cathode metals.

Developing green and high-efficient pyrometallurgy processes to recycle precious metals from spent lithium-ion batteries (LIBs) is of great importance for resource sustainability and environmental protection. Herein, a novel reduction roasting approach relying on spent LIB separator to refine the spent cathode is proposed. The efficiency of repurposing separator as a reductant for roasting the spent LiCoO2 cathode and the underlying mechanisms were investigated. After the separator-mediated roasting at 500 °C for 2 h, Li+ leaching efficiency of the cathode reached 93.2 %, >2.6 times higher than those after roasting without reductant (25.2 %) or with benchmark reductant graphite (26.1 %). Under the separator-added roasting condition, the cathode was converted to the desired products, CoO and Li2CO3. Based on the analysis of in-situ reaction using thermogravimetric/differential scanning calorimetry and pyrolysis gas species identification, the separator-mediated reduction roasting of cathode was composed of two stages, i.e., reducing gas generation due to separator pyrolysis, followed by the reducing gas mediated LiCoO2 reduction. During the process, the generated C2H4 and CO dominated the reduction. The use of co-existing separator to recover precious metals from spent LIBs is an effective and sustainable strategy to maximize the utilization of spent LIBs.

Boosting Reactive Oxygen Species Generation Using Inter-Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion.

Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4-electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H2 O2 and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter-facet edge (IFE) rich WO3 arrays in an electrolyte containing CO3 2- . Our results demonstrate that the IFE favors the adsorption of CO3 2- while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1-electron and indirect 2-electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 µmol h-1 with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value-added product.