Work Function Difference Research Articles

Tuning the selectivity of Pd-based catalysts for CO oxidative esterification: Regulating Pd's electronic effect

CO oxidative esterification is crucial in converting inorganic CO into organic oxygenated compounds within C1 chemistry and technology. However, understanding the structure-activity relationship underlying this reaction remains limited, primarily due to the entanglement of the Pd's geometric and electronic structures, which complicates selectivity control in practical applications. In this work, we design four Pd-based catalysts using the Al(111) motif to investigate their catalytic performance in CO oxidative esterification through density functional theory (DFT) calculations. Firstly, the larger lattice parameter of Al weakens horizontal Pd–Pd interactions while enhancing the vertical stability of Pd. Secondly, the electronic structure of Pd is locally regulated via charge transfer between subsurface and surface Pd, driven by their differences in work function. Our results indicate that the relative activity between CC coupling for dimethyl oxalate (DMO) and CO coupling for dimethyl carbonate (DMC) is primarily influenced by Pd's electronic effects, as revealed by energy barrier decomposition analysis. Thus, focusing on the regulation of Pd's electronic effects may offer a new strategy for controlling the selective oxidation esterification of CO.

Spontaneous built-in electric field in W-W2C@C heterostructure: Accelerating Sn2- directed migration in Li-S batteries

The commercialization of Li-S batteries is severely hindered by shuttle effect and sluggish redox reaction kinetics of LiPSs. Heterostructure can resolve the above shortcomings through the synergistic effect of adsorption and catalysis. However, long-chain LiPSs dissolving in electrolyte tend to cluster, resulting in low sulfur utilization and preventing kinetic conversion Thus, it is necessary to regulate the diffusion of Sn2− to achieve the directional diffusion from adsorbent to catalyst. Nevertheless, the design principle has not yet been clarified. W-W2C@C heterostructure with W of strong adsorption ability and high work function and W2C of excellent catalytic activity and low work function is designed by theoretical screening. Due to work function difference, this heterostructure controls the direction of the interface built-in electric field (BIEF), realizing the directional migration process of Sn2− from adsorptive W to catalytic W2C, thereby achieving a continuous “trapping-directional migration-conversion” reaction mechanism. The batteries have an excellent Li+ diffusion rate, high initial discharge specific capacity (1400.6 mAh/g at 0.2C), excellent rate capability (853.2 mAh/g at 2C), high reversible capacity (977.9 mAh/g after 150 cycles at 0.2C) and an extremely low capacity decay rate of 0.09 % per cycle after 300 cycles at 1C.

Investigating the role of internal electric fields on interfacial charge transfer dynamics in 2D MoSTe/WSeTe heterojunction for photocatalytic water splitting

Introducing the degrees of freedom brought by intrinsic dipole moments into heterojunctions allows for effective manipulation through the combination of different interfaces, thus offering more possibilities for designing high-performance photocatalysts. The influence of internal electric fields (EIN) in Janus materials on heterojunction interface charges is a crucial aspect of understanding the intrinsic mechanisms of charge transfer at interfaces. To address this, we construct four contact modes of MoSTe/WSeTe heterojunctions, considering the work function difference as a mediator to quantify two different electric fields. It is estimated that the influence of the interfacial electric field (EIF) on interfacial charge transfer is approximately 1.6 times that of the EIN (pointing outwards the interface). Moreover, the direction of the EIN varies, resulting in different impacts on interface charges. Subsequently, we also discuss the conditions under which different charge transfer modes are formed at different contact surfaces. On the other hand, the heterojunction of the Te-S mode can serve as a direct Z-Scheme photocatalyst for overall water splitting, and the presence of vacancies is necessary to address the issue of surface passivation. Our study not only refines the intrinsic mechanism of interfacial charge transfer in Janus-based heterojunctions but also predicts a direct Z-Scheme photocatalyst capable of achieving overall water splitting.

Coordination Tuning of FeNi-HMT Frameworks Derived Effective Hybrid Catalysts for Water Oxidation.

FeNi-based hybrid materials are promising oxygen evolution reaction (OER) catalysts for water electrolysis in hydrogen generation. In this work, the coordination tuning of FeNi-HMT frameworks was achieved by simply changing the Fe/Ni ratios using hexamethylenetetramine (HMT) as an organic ligand, and the derived hybrid FeNi catalysts with varied compositions were probed for OER. Incorporating varying amounts of Fe3+ by adjusting the Ni/Fe ratio results in different metal-organic framework (MOF) structures, and higher Fe feed leads to the formation of amorphous structures due to the coordination structure destruction from the weaker coordination capacity of Fe3+ compared to Ni2+ combining with the tertiary amine ligand. Among them, the FeNi-HMT (with the Fe/Ni molar ratio of 1/1) derived catalyst, consisting of Fe0.36Ni0.64 alloy/Ni0.4Fe2.6O4 spinel oxide heterostructures supported by graphitized carbon matrix, exhibits the highest OER performance. The unique structure facilitates significant electron transfer at the alloy/spinel interface due to the large work function difference between each phase. This strong electronic effect downshifts the d-band center of the catalyst and optimizes the binding energies to the crucial oxygenated intermediates, thereby promoting the OER kinetics. This work highlights the importance of the coordination tuning of FeNi-HMT frameworks for highly efficient catalyst development.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels

Photocatalytic CO2 reduction serves as an important technology for value‐added solar fuel production; however, it is generally limited by interfacial charge transport. To address this limitation, a two‐dimensional/two‐dimensional (2D/2D) p‐n heterojunction CuS‐Bi2WO6 (CS‐BWO) with highly connected and matched interfacial lattices was designed via a two‐step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p‐n heterojunction promoted electron transfer from the Cu to Bi sites, leading to coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in BWO nanosheets facilitated the adsorption and activation of CO2, and generation of high‐coverage key intermediate b‐CO32‐, while broad light‐harvesting CuS (CS) provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p‐n heterojunction CS‐BWO exhibited CO and CH4 yields of 135.7 and 62.5 µmol g‐1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS‐BWO nanosheets. This work provided an innovative design strategy for developing high‐activity heterojunction photocatalyst for converting CO2 into value‐added solar fuels.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels.

Photocatalytic CO2 reduction serves as an important technology for value-added solar fuel production; however, it is generally limited by interfacial charge transport. To address this limitation, a two-dimensional/two-dimensional (2D/2D) p-n heterojunction CuS-Bi2WO6 (CS-BWO) with highly connected and matched interfacial lattices was designed via a two-step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p-n heterojunctionpromotedelectron transfer from the Cu to Bi sites, leading to coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in BWO nanosheets facilitated the adsorption and activation of CO2, and generation of high-coverage key intermediate b-CO32-, while broad light-harvesting CuS (CS)provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p-n heterojunction CS-BWO exhibited CO and CH4 yields of 135.7 and 62.5 µmol g-1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS-BWO nanosheets. This work provided an innovative design strategy for developing high-activity heterojunction photocatalyst for converting CO2into value-added solar fuels.

MIL-125-PDI/ZnIn2S4 Inorganic-Organic S-Scheme Heterojunction With Hierarchical Hollow Nanodisc Structure for Efficient Hydrogen Evolution from Antibiotic Wastewater Remediation.

Efficient photocatalytic production of H2 from wastewater is expected to address environmental pollution and energy crises effectively. However, the rapid recombination of photoinduced carriers results in low photoconversion efficiency. At present, inorganic-organic S-scheme heterojunction have become a prominent and promising technology. In this study, an organic ligand modified MIL-125-PDI/ZnIn2S4 (ZIS) inorganic-organic S-scheme heterojunction catalyst is designed. ZIS nanosheets are grown on the disc-shaped MIL-125-PDI surface to form a distinctive hollow nanodiscs with hierarchical structure, giving the material an abundance of surface active sites, an optimized electronic structure, and a spatially separated redox surface. Consequently, the optimal 100MIL-125-PDI250/ZIS exhibited high photocatalytic HER of 508.99 µmol g-1 h-1 in Tetracycline hydrochloride (TC-HCl) solution. Meanwhile, the catalyst achieved complete TC-HCl removal and mineralization rate of 66.62% in 4h. Experimental and theoretical calculations corroborate that the staggered band alignment and work function difference between MIL-125-PDI and ZIS induce the formation of a built-in electric field, thus regulating the charge transfer routes and consequently enhancing charge separation efficiency. The possible photocatalytic mechanism is analyzed using liquid chromatography-mass spectrometry (LC-MS), and the toxicities of the degradation products are also evaluated. This work presents a green dual-function strategy for H2 production and antibiotic wastewater recycling.

Charge Transfer Plasmonics in Bespoke Graphene/α-RuCl3 Cavities.

Surface plasmon polaritons (SPPs) provide a window into the nano-optical, electrodynamic response of their host material and its dielectric environment. Graphene/α-RuCl3 serves as an ideal model system for imaging SPPs since the large work function difference between these two layers facilitates charge transfer that hole dopes graphene with n ∼ 1013 cm-2 free carriers. In this work, we study the emergent THz response of graphene/α-RuCl3 heterostructures using our home-built cryogenic scanning near-field optical microscope. Using phase-resolved imaging, we clearly observe long wavelength, heavily damped THz SPPs in a series of variable-size graphene cavities. From this, we extract the plasmonic wavelength and scattering rate in the graphene/α-RuCl3 heterostructures. We determine that the measured plasmon wavelength and electronic scattering rate match our heterostructures' theoretically predicted values. Our results demonstrate that shaping graphene into bespoke cavity structures enables observation and quantification of SPPs in heavily doped graphene that are largely not addressable with other experimental techniques. Moreover, the manifest lack of metallicity observed in the adjacent doped α-RuCl3 layer provides significant constraints on the nature of the interfacial charge transfer in this 2D heterostructure.

Built-in electric field-driven electron transfer behavior at Ru-RuP2 heterointerface fosters efficient and CO-resilient alkaline hydrogen oxidation

Exploiting a cost-effective electrocatalyst for hydrogen oxidation reaction (HOR) with high-performance and CO poisoning resistance is essential for the widespread application of alkaline anion exchange membrane fuel cells (AEMFCs). Herein, we craft a unique Ru-RuP2 heterostructure within hollow mesoporous carbon sphere (Ru-RuP2@C) using phosphide-controlled phase-transition approach. Benefiting from the interfacial electron transfer from RuP2 to Ru, the Ru-RuP2@C electrocatalyst exhibits impressive HOR performance with a mass activity of 2.87 mA μgRu−1. Notably, Ru-RuP2@C demonstrates strong tolerance to 1000 ppm CO, a capability lacking in PtRu/C and Pt/C. When serves as an anode catalyst for AEMFC, it achieves a peak power density of 521 mW cm−2, comparable to Pt/C. Experimental and theoretical analyses reveal that the built-in electric field, resulting from work function differences, creates an asymmetric charge distribution that modulates the d-band center of Ru-RuP2@C. This optimizes the adsorption strength of hydrogen and hydroxide intermediates, thereby accelerating HOR catalytic kinetics.

Understanding the Impact of SAM Fermi Levels on High Efficiency p-i-n Perovskite Solar Cells.

Completing the picture of the underlying physics of perovskite solar cell interfaces that incorporate self-assembled molecular layers (SAMs) will accelerate further progress in p-i-n devices. In this work, we modified the Fermi level of a nickel oxide-perovskite interface by utilizing SAM layers with a range of dipole strengths to establish the link between the resulting shift of the built-in potential of the solar cell and the device parameters. To achieve this, we fabricated a series of high-efficiency perovskite solar cells with no hysteresis and characterized them through stabilize and pulse (SaP), JV curve, and time-resolved photoluminescence (TRPL) measurements. Our results unambiguously show that the potential drop across the perovskite layer (in the range of 0.6-1 V) exceeds the work function difference at the device's electrodes. These extracted potential drop values directly correlate to work function differences in the adjacent transport layers, thus demonstrating that their Fermi level difference entirely drives the built-in potential in this device configuration. Additionally, we find that selecting a SAM with a deep HOMO level can result in charge accumulation at the interface, leading to reduced current flow. Our findings provide insights into the device physics of p-i-n perovskite solar cells, highlighting the importance of interfacial energetics on device performance.

Te2− modulated heterogeneous remodeling of S atoms in ultrathin ZnIn2S4 nanosheets containing S vacancies synergistically enhances CO2 photoreduction

Reconfiguration of in situ heterojunction composites without interfacial resistance by substitution of homologous anions for the formation of gradient work function differences inducing the formation of built-in electric field is an effective strategy to enhance the charge separation efficiency. Herein, Te2−/ZnIn2S4-VS (Te2−/ZIS-VS) in situ heterojunction was synthesized by substitution of Te2− ions for S2− in ultrathin ZIS containing S vacancies, which can significantly promote photogenerated charge separation, surface electron enrichment, and CO2 adsorption/activation. The presence of S vacancies and adjacent Te2−/S2− double anions, the double active sites constructed by defect engineering promote the desorption of *CO molecules while inhibiting the protonation toward *CHO, which was more favorable for selective CO2 photoreduction to CO. The experimental results showed that the CO yield of Te2−/ZIS-VS was significantly increased to 672.1 μmol g−1 h−1 compared with pristine ZIS (54.3 μmol g−1 h−1) and the CO selectivity was close to 83 %. Notably, the life cycle assessment (LCA) of Te2−/Znln2S4 nanosheets with S-vacancy was performed. The evaluation results showed that most of the 17 impact categories showed low overall impact values and were environmentally friendly. Based on the results of this LCA, suggestions were put forward to further optimize the product to reduce carbon emissions.

Co/CoTe heterostructure internal hairy fibers as high-efficiency oxygen electrocatalyst for Zn-air batteries

The design of highly efficient catalysts to enhance the kinetics of oxygen reduction (OER) and oxygen evolution (ORR) reactions is the key issue for the development of high-performance Zn-air battery. In this work, we report the design of Co-CoTe heterostructured fibers as the bifunctional oxygen catalyst for Zn-air battery. Firstly, the theoretical analysis was carried out on Co-CoTe heterostructure. The large work function difference is favorable to construct strong interfacial built-in electric field (BIEF), and the low energy barrier endows high catalytic activities. Moreover, the in-situ grown carbon shell was designed to build “core–shell” Co-CoTe/C unit to realize its high performance. They assemble the Co-CoTe@HFS fiber with good self-supporting and flexible features. Taken the advantages of the strong BIEF, the “core–shell” basic unit, and the freestanding substrate, the Co-CoTe@HFS fiber achieves the good electrocatalytic properties and high reliability. The full Zn-air battery (ZAB) with the Co/CoTe@HFS air cathode achieves the high peak power density and cycling stability over long-term cycling. Therefore, this work provides a clue to design bifunctional oxygen catalysts for high-performance ZABs.

Enhancement in photo-response of CuZnS nanocrystals-based photodetector using asymmetric work function electrodes

In this study, an efficient visible light photodetector has been fabricated by using heavy metal-free CuZnS Nanocrystals with average particle size of 13 ± 1 nm and has been synthesized by a microwave (MW) assisted synthesis technique. The optical band gap of this nanocrytstal is ∼1.7 eV and has an absorbance spectra ranging from 300 to700 nm. This low bandgap nanocrystals has been used to fabricate a photoconductor device with a CuZnS/ZnO bilayer structure. Besides, the device performance has been enhanced by using an asymmetric work-function lateral electrodes. The work-function difference between the electrodes gives a driven voltage between the electrodes, which allows faster collection of charge carriers from the device. As a consequence, a significant photocurrent is generated by the device even without any external bias. The self-biased (at 0 V) external quantum efficiency (EQE) of this device is ∼ 4 % (at 430 nm) whereas this value reaches ∼ 20 % under 2 V external bias. The device possesses the responsivity (Rλ) and detectivity (D) of 8.8 A/W and 3.8 × 1012 Jones at 320 nm respectively under 2 V external bias.

Constructing hollow cobalt sulfide nanocages strung by manganese molybdate nanorods for high-efficiency supercapacitors and electrocatalytic methanol oxidation

Constructing core-shell heterostuctures with rationally designed nanoarchitectures and components is a promising strategy to pursuit high-efficiency energy storage and conversion in supercapacitors (SCs) and direct methanol fuel cells (DMFCs). Herein, a multi-dimensional MnMoO4@CoS core-shell heterostructure is designed and synthesized by stringing metal-organic framework-derived hollow CoS nanocages with MnMoO4 nanorods. Such heterostructure provides more electroactive sites and enhanced structural stability. Theory calculations unveil that the work function difference between MnMoO4 and CoS induces the charge redistribution and modulate interfacial electronic configuration in the MnMoO4/CoS heterojunction. Meanwhile, a interfacial built-in electrical field is established, enhancing interfacial charge transfer efficiency and promoting the surface adsorption of electrolyte ions. By integrating all these advantages, the MnMoO4@CoS electrode demonstrates enhanced rate capacities (933 C g−1 at 1 A g−1 and 623 C g−1 at 10 A g−1) and cycling durability (90.3 % capacity retention after 10,000 cycles) compared to bare MnMoO4 and CoS electrodes. Moreover, the MnMoO4@CoS electrode exhibits an appreciable electrocatalytic performance for methanol oxidation, with a current density of 294.8 mA cm−2 at 10 mV s−1 and 96.6 % current retention after 10,000 s. Our work offers a fundamental guideline for designing and engineering core-shell heterostructures with desirable electrochemical performance for SCs and DMFCs.

Engineering of MnTe/MnO Heterostructures with Interfacial Electric Field Modulation for Efficient and Durable Li–O2 Batteries

AbstractDesign and synthesis of highly active and robust bifunctional cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are of vital significance for practical applications of lithium–oxygen (Li–O2) batteries. Herein, a built‐in electric field (BIEF) strategy is reported to fabricate MnTe/MnO heterostructures with a large work function difference (ΔΦ) as a bifunctional cathode catalyst in Li–O2 batteries. The MnTe/MnO heterostructures with nanosheets and microporous structures result in an abundance of exposed active sites and facilitate mass transfer. More importantly, the heterogeneous MnTe/MnO nano‐interface region provides a BIEF that can trigger interfacial charge redistribution, fine‐tune the adsorption energy of oxygen intermediates, and alter the morphology of discharge products to accelerate ORR/OER kinetics. Impressively, the fabricated Li–O2 batteries with MnTe/MnO cathode showcases exhibit excellent electrochemical performances, including low charging overpotential, a high specific capacity of 11930 mA h g−1, and good cycle stability over 350 cycles even with a fixed specific capacity of 500 mA h g−1 at a current density of 500 mA g−1. This work provides an avenue for the rational design of high performance heterostructure electrocatalysts toward practical applications for rechargeable Li–O2 batteries.

Study on Two Inorganic Consumables in PMMA Electrochromic Devices Based on Work Function Differences

In electrochromic devices, the dielectric layer is not only an electrode dielectric, but also can provide compensating ions for electrochromism. In this paper, three composite porous materials, PMMA/SiO2, PMMA/TiO2, and PMMA/SiO2/TiO2, were prepared and assembled using polymethyl cellulose (PMMA) as the polymer matrix, impurity medium (SiO2) and titanium dioxide (TiO2) inorganic polymers, and the effect of doping two inorganic porous materials on the electrochromic performance was studied. The optical recovery and cycle stability of electrochromic wear of the PMMA/SiO2/TiO2 composite structure are significantly improved compared with the loss of other ceramic structures. Cyclic voltammetry analysis shows that the lithium ion diffusion coefficient of the electrochromic device using the PMMA/SiO2/TiO2 composite ceramic structure is the largest, which is 2.5 × 10−14 cm2​ s−1 . The improvement of electrochromic performance is mainly due to the difference in work function between SiO2 and TiO2 on the figure of merit diagram, which leads to the directional movement of the resonator, accelerates the transmission rate of Li+ and further optimizes the electrochemical properties of the composite ceramic. This study provides an effective method to improve the performance of electrochromic devices.

A comparative study on the electrical properties of Ba0.6Sr0.4TiO3 film capacitors with different top electrodes

Au/Ba0.6Sr0.4TiO3 (BST)/La0.5Sr0.5CoO3 (LSCO) and Pt/BST/LSCO ferroelectric capacitors were successfully constructed on (001) LaAlO3 substrates via off-axis magnetron sputtering. X-ray diffraction (XRD) and Phi scan patterns confirmed that the BST film was epitaxial with an out-of-plane tetragonal phase. The ferroelectric and dielectric measurements reveal that, compared with the Pt/BST/LSCO capacitor, the Au/BST/LSCO capacitor exhibits a larger coercive field (∼139.7 kV/cm), smaller permanent polarization (∼2.94 μC/cm2), and lower tunability (∼65.22 %), which may be attributed to the higher difference in work function and weaker depolarization field screen effect of the top electrode, as well as smaller interfacial capacitance of the Au/BST interface than those of the Pt/BST interface. Therefore, based on series capacitor model and leakage behavior analysis, the thickness and dielectric constant of interfacial layer are quantitatively determined to be 3.52 nm and 12.13 for Pt/BST, and 4.42 nm and 5.82 for Au/BST, respectively. Our results pave a way for improving the dielectric performance in electrically tunable microwave devices.

Engineering a Ce Promoter into a Three-Dimensional Porous Mo2C@NC Heterostructure for Hydrogen Evolution Electrocatalysis via Weakening the Mo-H Bond Strength.

The pursuit of highly efficient electrocatalysts for the alkaline hydrogen evolution reaction (HER) is of paramount importance for water splitting. However, it is still a formidable task in Mo2C-based materials because of the agglomeration and strong Mo-H binding of Mo2C units. Herein, a novel CeOCl-CeO2/Mo2C heterostructure nesting within a three-dimensional porous nitrogen-doped carbon matrix has been designed and used for catalyzing HER via simultaneous morphology and heterointerface engineering. As expected, the optimal CeOCl-CeO2(0.2)/Mo2C@3DNC exhibits impressive HER activity, with a low overpotential of 156 mV at a current density of 10 mA cm-2 coupled with a slight Tafel slope of 62.20 mV dec-1. Introducing a Ce promoter, that is CeOCl and CeO2, would endow the interface with an internal electric field and electron redistribution between CeOCl-CeO2 and Mo2C induced by the heterogeneous work function difference. Moreover, experimental investigation and density functional calculations confirm that the CeOCl-CeO2/Mo2C heterointerface can downshift the d-band center of the active Mo center, weakening the strength of the Mo-H coupling. This proposed concept, engineering Ce-based promoters into active entities involved in the heterostructure to modulate intermediate adsorption, offers a great opportunity for the design of superior electrocatalysts for energy conversion.

Engineering MOF@LDH heterojunction with strong interfacial built-in electric field towards enhanced electrocatalytic water oxidation

Guiding the dynamic reconstruction of the oxygen evolution reaction (OER) is crucial for realizing the industrial application of hydrogen production through water electrolysis. In this study, we have intricately designed a built-in electric field (BIEF) between MIL-88B(Fe) and layered double hydroxide (LDH) with an adjusted work function difference. This design drives an asymmetric interfacial electron distribution, enhancing electron accumulation at the Fe sites within MIL-88B(Fe) and electron-deficient LDHs. Consequently, this setup promotes the surface dynamic reconstruction of LDHs into highly active oxyhydroxides, while simultaneously slowing down the rapid dissolution of Fe during OER operation. This optimization improves the adsorption/desorption of oxygen intermediates, ensuring a sustained high OER activity during long-term electrochemical operation. As expected, the optimal MIL-88B(Fe)@NiCo LDH configuration demonstrates a remarkably low overpotential of only 279 mV at 10 mA cm−2, maintaining operational stability for 70 h. This research significantly advances our understanding of the dynamic reconstruction of MOF@LDH heterojunctions and introduces a straightforward strategy for engineering BIEF to guide this process effectively.

Architecting Ni3Se4-NiSe2-Co3O4 Triple-Interface Heterostructure on MXene Nanosheets for Boosting Water Splitting by Electronic Modulation and Interface Effects.

Strategically engineering electrocatalysts with optimized interfacial electronic architectures and accelerated reaction dynamics is pivotal for augmenting hydrogen generation via alkaline water electrolysis on an industrial scale. Herein, a novel triple-interface heterostructure Ni3Se4-NiSe2-Co3O4 nanoarrays are designed anchored on Ti3C2Tx MXene (Ni3Se4-NiSe2-Co3O4/MXene) with significant work function difference (ΔΦ) as bifunctional electrocatalysts for water electrolysis. Theoretical calculations combined with experiments uncover the pivotal role of the interface-induced electric field in steering charge redistribution, which in turn modulates the adsorption and desorption kinetics of reaction intermediates. Furthermore, the synergistic interaction between Ni3Se4-NiSe2-Co3O4 and Ti3C2Tx MXene nanosheets endows the hybrids with a large electrochemical surface area, abundantly active sites, and high conductivity. Thus, Ni3Se4-NiSe2-Co3O4/MXene manifests exceptional catalytic prowess for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In addition, the Ni3Se4-NiSe2-Co3O4/MXene electrocatalyst in the water electrolyzer delivers excellent performance and maintains commendable stability beyond 100h of electrocatalytic operation.