Ultralow Cell Voltage Research Articles

Engineering multiple nano-twinned high entropy alloy electrocatalysts toward efficient water electrolysis

Inducing defects in high entropy alloys (HEAs) has been recognized as a promising approach for tuning surface energetics and catalytic activities. However, the comprehensive understanding and facile synthetic methods for defect-rich HEAs remain challenging. Herein, we present an interstitial-atom engineering strategy that involves interstitial atom doping to synthesize B-doped FeCoNiCuMoB HEA films containing abundant multiple nano-twin boundaries. The resulting fivefold-twinned FeCoNiCuMoB catalyst exhibits exceptional performance in alkaline hydrogen evolution reaction (HER, 26mV at -10 mA cm-2) and oxygen evolution reaction (OER, 201mV at 10mAcm-2). Notably, the two-electrode electrolyzer composed of the FeCoNiCuMoB film electrodes achieved the 10mAcm-2 at an ultralow cell voltage (1.48V) for water electrolysis, simultaneously maintaining long-term durability. Through in-situ Raman spectroscopy, X-ray absorption spectroscopy (XAS), electrochemical analyses, and density functional theory (DFT) calculations, we elucidate that the unique twin boundaries play a crucial role in tailoring surficial electronic structures. Moreover, election-rich B atoms display optimized atomic configurations, synergistically contributing to a thermodynamically favourable HER/OER pathway. This work provides a platform via interstitial-atom engineering for designing exceptional HEA catalysts, integrating planar defects and electronic effects, to enhance the efficiencies in water electrolysis applications.

Ir Doping Modulates the Electronic Structure of Flower-Shaped Phosphides for Water Oxidation.

Electrolysis of water to produce hydrogen is an efficient, clean, and environmentally friendly hydrogen production method with unlimited development prospects. However, its overall efficiency is hampered by the slow oxygen evolution reaction (OER) with complex electron transfer processes. Therefore, designing efficient and low-cost OER catalysts is the key to solving this problem. In this paper, Ir-doped Co2P/Fe2P (abbreviated as Ir-CoFeP/NF) was grown on nickel foam through the strategies of low amount noble-metal doping and mild phosphating. Phosphide derived from a floral metal-organic framework (MOF) exhibits regular three-dimensional (3D) morphology and large active area, avoiding the stacking of active sites. The addition of Ir can effectively adjust the electronic structure, change the position of the d-band center, and increase active sites, thus enhancing the catalytic activity. Hence, the optimized catalyst exhibits unexpected electrocatalytic OER activity with an ideal overpotential of 213 mV at 10 mA cm-2, as well as a low Tafel slope of 40.63 mV dec-1. Coupling with Pt/C for overall water splitting (OWS), the entire device only needs an ultralow cell voltage of 1.50 V to achieve a current density of 10 mA cm-2. Besides, the OWS can be maintained for more than 70 h. This study demonstrates the superiority of Ir-doped phosphide in accelerating water oxidation.

Electrochemical oxidation synthesis of energetic compound coupled with energy-efficient hydrogen evolution

Electrocatalytic water splitting process involves hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), where OER is a high energy-consumption step. Electro-oxidation of small molecules instead of OER and coupled with HER is a potential strategy for changing this situation. This work describes a coupling system for synthesizing energetic compounds (EMs) and hydrogen production using a ruthenium-doped nickel diselenide catalyst on carbon fiber paper (CFP@NiSe2@Ru). The coupling system was established to combine 3,4-diaminofurozan (DAF) oxidation with overall water splitting (OWS). It was achieved to an ultra-low cell voltage of 1.30 V at 10 mA cm–2 for 3,3′-diamino-4,4′-azofurazan (DAAF) green synthesis and hydrogen production simultaneously. This work established a new path towards the energy-efficient generation of H2 and the green electrosynthesis of DAAF.

Sabatier principle based design of high performance FeCoNiMnMoP high entropy electrocatalysis for alkaline water splitting

FeCoNi-based high entropy intermetallic compounds are promising substitutes for noble metal catalysts for hydrogen evolution reaction (HER) and oxygen evolution (OER), while their activity is restricted by the synergistic effect between the elements. In this paper, the theoretical model of FeCoNiMnMoP bifunctional catalyst has been reasonably designed given the volcanic curve of M−H bond energy as a valuable guide for candidate metal elements. Theoretical calculations show that the synergistic effect between multiple sites not only accelerates the electron transfer but also reduces the rate-determining step (RDS) barrier. At the same time, the introduction of Mo also enhances the total density of states and reduces the d-band center, thus optimizing the adsorption and dissociation of intermediates. The experimental results confirm that the theoretical model has excellent catalytic performance. In the alkaline solution, FeCoNiMnMoP‖FeCoNiMnMoP requires only an ultra-low cell voltage of 1.49 V for overall water splitting when the current density is 10 mA cm−2. In general, novel insights on the effects of intermetallic synergies on water decomposition are provided, which is helpful for the design of bifunctional catalysts based on volcanic diagrams.

Interfacial and Vacancy Engineering on 3D-Interlocked Anode Catalyst Layer for Achieving Ultralow Voltage in Anion Exchange Membrane Water Electrolyzer.

Developing a high-efficiency and stable anode catalyst layer (CL) is crucial for promoting the practical applications of anion exchange membrane (AEM) water electrolyzers. Herein, a hierarchical nanosheet array composed of oxygen vacancy-enriched CoCrOx nanosheets and dispersed FeNi layered double hydroxide (LDH) is proposed to regulate the electronic structure and increase the electrical conductivity for improving the intrinsic activity of the oxygen evolution reaction (OER). The CoCrOx/NiFe LDH electrodes require an overpotential of 205 mV to achieve a current density of 100 mA cm-2, and they exhibit long-term stability at 1000 mA cm-2 over 7000 h. Notably, a breakthrough strategy is introduced in membrane electrode assembly (MEA) fabrication by transferring CoCrOx/NiFe LDH to the surface of an AEM, forming a 3D-interlocked anode CL, significantly reducing the overall cell resistance and enhancing the liquid/gas mass transfer. In AEM water electrolysis, it exhibits an ultralow cell voltage of 1.55 Vcell to achieve a current density of 1.0 A cm-2 in 1 M KOH, outperforming the state-of-the-art Pt/C//IrO2. This work provides a valuable approach to designing high-efficiency electrocatalysts at the single-cell level for advanced alkaline water electrolysis technologies.

Electron Manipulation and Surface Reconstruction of Bimetallic Iron-Nickel Phosphide Nanotubes for Enhanced Alkaline Water Electrolysis.

Developing high-efficiency and stable bifunctional electrocatalysts for water splitting remains a great challenge. Herein, NiMoO4 nanowires as sacrificial templates to synthesize Mo-doped NiFe Prussian blue analogs are employed, which can be easily phosphorized to Mo-doped Fe2xNi2(1-x)P nanotubes (Mo-FeNiP NTs). This synthesis method enables the controlled etching of NiMoO4 nanowires that results in a unique hollow nanotube architecture. As a bifunctional catalyst, the Mo-FeNiP NTs present lower overpotential and Tafel slope of 151.3 (232.6) mV at 100 mA cm-2 and 76.2 (64.7) mV dec-1 for HER (OER), respectively. Additionally, it only requires an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water splitting and can steadily operate for 200 h at 100 mA cm-2. First-principles calculations demonstrate that Mo doping can effectively adjust the electron redistribution of the Ni hollow sites to optimize the hydrogen adsorption-free energy for HER. Besides, in situ Raman characterization reveals the dissolving of doped Mo can promote a rapid surface reconstruction on Mo-FeNiP NTs to dynamically stable (Fe)Ni-oxyhydroxide layers, serving as the actual active species for OER. The work proposes a rational approach addressed by electron manipulation and surface reconstruction of bimetallic phosphides to regulate both the HER and OER activity.

Self-supported iron-doped nickel oxide multifunctional electrodes for highly efficient energy storage and overall water-splitting uses

Caused by complex synthesis processes, slow diffusion rates, and the formation of undesired nanostructures, it is tedious to produce a high-quality nickel oxide (NiO) electrodes for potential energy storage and water splitting applications. This paper introduces a novel chemical technique for producing self-supported iron-doped NiO electrodes having a high concentration of oxygen vacancies by utilizing different iron-based salts i.e. iron nitrate, iron chloride, iron ammonium sulfate, iron fumarate, and iron sulfate salts. After examining physical properties, the electrochemical energy storage and water splitting measurements were performed where iron nitrate precursor-mediated self-supporting Fe-NiO electrode confirms the optimum performance. Specifically, it exhibits a specific capacitance (SC) of 3302.5 Fg−1 at a current density of 5 Ag−1. The as-fabricated Fe-NiO-A//Bi2O3 asymmetric supercapacitor has a broad voltage range of 1.5 V, a remarkable volumetric-energy-density of 98.2 W hkg−1 at a power density of 900 Wkg−1, and a long-lasting cycling life with 92.6 % capacity retention after 5000 cycles at a current density of 15 Ag−1. A bifunctional Fe-NiO//Fe-NiO electrocatalyst demonstrates a current density of 10 mA cm−2 and remarkable long-term durability of 75 h without any degradation while operating at an ultra-low cell voltage of only 1.51 V, specifying importance of self-supported Fe-doped NiO electrodes for electrochemical energy storage and water splitting applications.

Metallic Cu-incorporated NiFe layered double hydroxide nanosheets enabling energy-saving hydrogen generation from chlorine-free seawater electrolysis coupled with sulfion upcycling

Development of multifunctional non-noble electrocatalysts for seawater electrolysis is imperative but still challenging for scale-up hydrogen production to avoid harmful chlorine chemistry. Herein, the metallic Cu-incorporated NiFe layered double hydroxide (LDH) nanosheets are prepared by a facile consecutive corrosion strategy using iron foam (IF) as a reactive substrate, which enable the corrosion-resistant and chlorine-free seawater electrolysis combined with anodic sulfion oxidation for energy-efficient hydrogen production at ultralow electricity consumption. The NiFe-LDH/Cu-IF exhibits excellent electrocatalytic activities for hydrogen evolution reaction (HER) and sulfion oxidation reaction (SOR), achieving low potentials of 0.203 and 0.310 V (vs RHE) at 100 mA cm−2 in alkaline seawater, respectively. The assembled hybrid HER||SOR seawater electrolyzer realizes the ultra-low cell voltage of 0.619 V and power consumption of 1.48 kWh/m3 H2 at 50 mA cm−2, cutting energy consumption over 67 % compared to conventional seawater electrolysis.

Rational Design of FeCo-S/Ni2P/NF Heterojunction as a Robust Electrocatalyst for Water Splitting.

The rational design of nonnoble-metal-based catalysts with high electroactivity and long-term stability, featuring controllable active sites, remains a significant challenge for achieving effective water electrolysis. Herein, a heterogeneous catalyst with a FeCo-S and Ni2P heterostructure (denoted FeCo-S/Ni2P/NF) grown on nickel foam (NF) was synthesized by a solvothermal method and low-temperature phosphorization. The FeCo-S/Ni2P/NF catalyst shows excellent electrocatalytic performance and stability in alkaline solution. The FeCo-S/Ni2P/NF catalyst demonstrates low overpotentials (η) for both the hydrogen evolution reaction (HER) (49 mV@10 mA cm-2) and the oxygen evolution reaction (OER) (279 mV@100 mA cm-2). Assembling the FeCo-S/Ni2P/NF catalyst as both cathode and anode in an electrolytic cell for overall water splitting (OWS) needs an ultralow cell voltage of 1.57 V to attain a current density (CD) of 300 mA cm-2. Furthermore, it demonstrates excellent durability, significantly outperforming the commercial Pt/C∥IrO2 system. The results of experiments indicate that the heterostructure and synergistic effect of FeCo-S and Ni2P can significantly enhance conductivity, facilitate mass/ion transport and gas evolution, and expose more active sites, thereby improving the catalytic activity of the electrocatalyst for the OWS. This study provides a rational approach for the development of commercially promising dual-functional electrocatalysts.

Iron Molybdenum Sulfide‐Supported Ultrafine Ru Nanoclusters for Robust Sulfion Degradation‐Assisted Hydrogen Production

AbstractElectrocatalytic hydrogen evolution and (S2−) recycling present promising strategies for cost‐effective hydrogen production and simultaneous removal of environmental pollutants. However, the advancement of this technology is hindered by the limited availability of affordable, efficient, and stable catalysts. Herein, the study synthesizes ultrafine ruthenium (Ru) nanoclusters on a substrate of iron molybdenum sulfide (FeMo‐S) nanosheets, creating a new heterointerface catalyst (FeMo‐S/Ru) for the hydrogen evolution reaction (HER) and sulfion oxidation reaction (SOR). Experimental and theoretical calculations suggest that strong electron interactions between Ru nanoclusters and FeMo‐S substrate, optimizing *H adsorption and promoting HER activity on one side while facilitating the production and adsorption of sulfur intermediates on the other side, effectively catalyzing SOR. Additionally, the assembled electrocatalytic coupling system with FeMo‐S/Ru displays an ultralow cell voltage of 0.57 V at 100 mA cm−2, achieving high Faradaic efficiencies (>96%) for H2 production, while also exhibiting remarkable durability over 1 month (838 h). This work paves the way for the development of highly efficient and durable supported catalysts, enabling energy‐saving hydrogen production and environmentally friendly sulfion recycling.

Rational Construction of 3D Self-Supported MOF-Derived Cobalt Phosphide-Based Hollow Nanowall Arrays for Efficient Overall Water Splitting At large Current Density.

Developing efficient nonprecious bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) in the same electrolyte with a low overpotential and large current density presents an appealing yet challenging goal for large-scale water electrolysis. Herein, a unique 3D self-branched hierarchical nanostructure composed of ultra-small cobalt phosphide (CoP) nanoparticles embedded into N, P-codoped carbon nanotubes knitted hollow nanowall arrays (CoPʘNPCNTs HNWAs) on carbon textiles (CTs) through a carbonization-phosphatization process is presented. Benefiting from the uniform protrusion distributions of CoP nanoparticles, the optimum CoPʘNPCNTs HNWAs composites with high abundant porosity exhibit superior electrocatalytic activity and excellent stability for OER in alkaline conditions, as well as for HER in both acidic and alkaline electrolytes, even under large current densities. Furthermore, the assembled CoPʘNPCNTs/CTs||CoPʘNPCNTs/CTs electrolyzer demonstrates exceptional performance, requiring an ultralow cell voltage of 1.50V to deliver the current density of 10mAcm-2 for overall water splitting (OWS) with favorable stability, even achieving a large current density of 200mAcm-2 at a low cell voltage of 1.78V. Density functional theory (DFT) calculation further reveals that all the C atoms between N and P atoms in CoPʘNPCNTs/CTs act as the most efficient active sites, significantly enhancing the electrocatalytic properties. This strategy, utilizing 2D MOF arrays as a structural and compositional material to create multifunctional composites/hybrids, opens new avenues for the exploration of highly efficient and robust non-noble-metal catalysts for energy-conversion reactions.

Ru nanoparticles immobilized on self-supporting porphyrinic MOF/nickel foam electrode for efficient overall water splitting

To achieve carbon neutrality, the development of effective and durable electrodes for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of utmost importance. Herein, the Ru3.4-PMOF/NF electrode was successfully prepared by immobilizing Ru nanoparticles on porphyrinic metal-organic framework/nickel foam (PMOF/NF), effectively driving both the OER and the HER in an alkaline electrolyte. To achieve 10 mA cm−2, the Ru3.4-PMOF/NF electrode only required overpotentials of 19 and 215 mV for HER and OER, respectively. For overall water splitting, an ultra-low cell voltage of 1.468 V was required to drive 10 mA cm−2, surpassing the performance of the integrated Pt/C and RuO2 couple electrode (1.6627 V). The outperformed electrocatalytic activity could be ascribed to the well-dispersed Ru nanoparticles, the self-reconstruction of PMOF, the synergistic effect, and the lamellar morphology. This study offers a promising approach for the development of ruthenium-doped electrodes that can enhance the efficiency of electrocatalytic water splitting.

Porous Flower-Like Nanoarchitectures Derived from Nickel Phosphide Nanocrystals Anchored on Amorphous Vanadium Phosphate Nanosheet Nanohybrids for Superior Overall Water Splitting.

Transition metal phosphides (TMPs) and phosphates (TM-Pis) nanostructures are promising functional materials for energy storage and conversion. Nonetheless, controllable synthesis of crystalline/amorphous heterogeneous TMPs/TM-Pis nanohybrids or related nanoarchitectures remains challenging, and their electrocatalytic applications toward overall water splitting (OWS) are not fully explored. Herein, the Ni2P nanocrystals anchored on amorphous V-Pi nanosheet based porous flower-like nanohybrid architectures that are self-supported on carbon cloth (CC) substrate (Ni2P/V-Pi/CC) are fabricated by conformal oxidation and phosphorization of pre-synthesized NiV-LDH/CC. Due to the unique microstructures and strong synergistic effects of crystalline Ni2P and amorphous V-Pi components, the obtained Ni2P/V-Pi/CC owns abundant active sites, suitable surface/interface electronic structure and optimized adsorption-desorption of reaction intermediates, resulting in outstanding electrocatalytic performances toward hydrogen and oxygen evolution reactions in alkaline media. Correspondingly, the assembled Ni2P/V-Pi/CC||Ni2P/V-Pi/CC electrolyzer only needs an ultralow cell voltage (1.44V) to deliver 10mA cm-2 water-splitting currents, exceeding its counterparts, recently reported bifunctional catalysts-based devices, and Pt/C/CC||IrO2/CC pairs. Moreover, the Ni2P/V-Pi/CC||Ni2P/V-Pi/CC manifests remarkable stability. Also, such device shows a certain prospect for OWS in acidic media. This work may spur the development of TMPs/TMPis-based nanohybrid architectures by combining structure and phase engineering, and push their applications in OWS or other clean energy options.

Local-reconstruction enables cobalt phosphide array with bifunctional hydrogen evolution and hydrazine oxidation

Coupling hydrazine electrooxidation with hydrogen evolution reaction (HER) attracts ever-growing attention for energy-saving H2 production. However, the performance of hydrazine-assisted HER unit is restricted by the bifunctional catalysts with un-fully activated sites. Herein, a surface local-reconstruction strategy is proposed to integrate amorphous Co(OH)2 and P vacant CoP into the CoH-CoPV@CFP catalyst. The inherent electron-deficient Co sites in Co(OH)2 show strong N-Co interaction to accelerate the N2H4 dehydrogenation kinetics, while the as-formed P vacancies in CoP play a crucial role in moderating the H* adsorption energy, the excellent bifunctionality thus being obtained. Specifically, it achieves the low overpotentials of − 77 and − 61 mV at 10 mA cm−2 for HER and HzOR in alkaline media, respectively. A lab-scale electrolyzer can deliver the industrial-grade current density of 500 mA cm−2 under ultralow cell voltage of 0.23 V. This local-reconstruction strategy may pave new avenue to design efficient catalysts for hydrazine-assisted H2 generation.

Highly durable monolithic electrode for water electrolysis at industrial current densities

The development of highly durable electrode with current density over 500 mA cm−2 is the key to realize low-energy-cost industrial water electrolysis. While the dramatical gas evolution environment with high current makes the electrode more likely to suffer from severe dropping and loss of catalytic active components. Hence, it is of great significance but challenge to develop robust monolithic electrode with both high activity and durability in water electrolysis. Herein, we design an edge-rich monolithic electrode via in-situ construction of molybdenum disulfide and nickel disulfide heterogeneous interfaces on nickel foam (ER-MoSNi) for extraordinary water electrolysis. The bifunctional ER-MoSNi monolithic electrode incorporated two-electrode water electrolyzer with 1.0 M KOH solution at 25 °C requires ultralow cell voltage of 2.08 V@1000 mA cm−2, far exceeding the Pt/C supported on nickel foam as cathode and IrO2 supported on nickel foam as anode of 2.6 V@1000 mA cm−2. Moreover, the ER-MoSNi monolithic electrode can operate stably for over 2500 h at a current density of 1000 mA cm−2, which is significant super to Pt/C║IrO2. The great advantages of the ER-MoSNi monolithic electrode in the activity and durability have shown great potential in the field of industrial water electrolysis.

Crystalline Ni5P4/amorphous CePO4 core/shell heterostructure arrays for highly-efficient electrocatalytic overall water splitting

Exploring low-cost and highly efficient bifunctional electrocatalysts for overall water splitting has become a research focus recently. Crystalline/amorphous core/shell heterostructures have great potential for applications in the field of electrocatalytic overall water splitting. However, related research is still challenging. Herein, crystalline Ni5P4 nanosheets/amorphous CePO4 nanocrystals core/shell heterostructure arrays were developed for electrocatalytic overall water splitting. It is shown that the heterostructure array required competitive HER and OER overpotentials of 94 and 191 mV in alkaline environment (10 mA/cm2), respectively. Encouragingly, the symmetrical two-electrode system constructed with the heterostructure array only required an ultra-low cell voltage of 1.535 V to achieve a current density of 10 mA/cm2. This indicates the system has huge potential in overall water splitting. The electrocatalytic mechanism was studied systematically by combining theoretical calculation and experimental characterization. It was found that the surface coating of amorphous CePO4 could not only significantly increase the electrochemical active surface area and improve the charge transfer of crystalline Ni5P4 nanosheets, but could also regulate d-band center of Ni5P4 and optimize the adsorption towards reaction intermediates in water splitting. The results not only provide an excellent crystalline/amorphous core/shell heterostructure bifunctional electrocatalyst for overall water splitting but also greatly expand the application of rare earth metal phosphate CePO4.

Iron-doped cobalt nitride as an efficient electrocatalyst towards energy saving hydrazine assisted seawater splitting in near neutral to highly alkaline pH achieving industry level current density

Replacing sluggish anodic oxygen evolution reaction by hydrazine oxidation reaction in seawater electrolysis is one of the smartest ways of getting multiple benefits as it offers an energy saving route for hydrogen production keeping the cell voltage way smaller than responsible voltage for corrosive chloride oxidation. Here, we report iron-doped Co3N as highly active electrocatalyst towards hydrazine oxidation reaction and hydrogen evolution reaction in wide pH range of 7–14. The two-electrode electrolyser system reached industry scale current density of 1000 mA cm−2 at ultralow cell voltage of 0.65 V, and found sustainable at 500 mA cm−2 over 95 h in hydrazine assisted alkaline seawater splitting. The electrolyser system also achieved 200 mA cm−2 current density at 0.75 V in hydrazine assisted neutral seawater medium. Interestingly, a thin amorphous iron oxide layer formed in Fe-doped Co3N provided much needed protection during electrocatalysis offering long term stability at industry level current density.

Hierarchical electronic coupling engineering of bimetallic sulfide driven by CoFe bimetal MOFs anchored on MXene promotes efficient overall water splitting

Rational design cost-effective water-splitting catalysts are essential for current energy storage and conversion. Here, we ingeniously design alloy-phase bimetallic sulfides anchored on the conductive substrate MXene, obtained by a facile topological hydrothermal sulfide method of self-template sacrifice using bimetallic MOFs. Density functional theory calculations (DFT) and related material characterization demonstrate that electron rearrangement at the atomic/orbital level and hierarchical electronic coupling between Schottky heterostructures of MXene boosts charge transfer efficiency, the asymmetric 3d electronic structure of the Co-Fe atoms optimizes the d-band center value εd of the Co8FeS8 MXene/NF. Thus, the efficient composite electrocatalyst of Co8FeS8 MXene/NF with multi-metal active sites exhibits extraordinary electrocatalytic performance with remarkably low overpotentials of 171 mV (OER) and 108 mV (HER) at 10 mA cm−2, respectively. Notably, when used in 1 M KOH electrolytic cell, Co8FeS8 MXene/NF also accelerate overall water splitting at an ultra-low cell voltage of only 1.51 V at 10 mA cm−2, far exceeding that of standard Pt-C/NF//RuO2/NF electrodes (1.59 V). This work gives an effective strategy to construct MOF-derived alloy-phase bimetallic sulfides and improve the intrinsic activity of alloy-phase bimetallic sulfides electrochemical catalysts.

Charge Self-Regulation of Metallic Heterostructure Ni2 P@Co9 S8 for Alkaline Water Electrolysis with Ultralow Overpotential at Large Current Density.

Designing cost-effective alkaline water-splitting electrocatalysts is essential for large-scale hydrogen production. However, nonprecious catalysts face challenges in achieving high activity and durability at a large current density. An effective strategy for designing high-performance electrocatalysts is regulating the active electronic states near the Fermi-level, which can improve the intrinsic activity and increase the number of active sites. As a proof-of-concept, it proposes a one-step self-assembly approach to fabricate a novel metallic heterostructure based on nickel phosphide and cobalt sulfide (Ni2 P@Co9 S8 ) composite. The charge transfer between active Ni sites of Ni2 P and Co─Co bonds of Co9 S8 efficiently enhances the active electronic states of Ni sites, and consequently, Ni2 P@Co9 S8 exhibits remarkably low overpotentials of 188 and 253mV to reach the current density of 100mAcm-2 for the hydrogen evolution reaction and oxygen evolution reaction, respectively. This leads to the Ni2 P@Co9 S8 incorporated water electrolyzer possessing an ultralow cell voltage of 1.66 V@100mAcm-2 with ≈100% retention over 100h, surpassing the commercial Pt/C║RuO2 catalyst (1.9 V@100mAcm-2 ). This work provides a promising methodology to boost the activity of overall water splitting with ultralow overpotentials at large current density by shedding light on the charge self-regulation of metallic heterostructure.

Formaldehyde oxidation boosts ultra-low cell voltage industrial current density water electrolysis for dual hydrogen production

The high cost is a major issue that has contributed to the slow industrialization of electrolytic water. To reduce the cell voltage to below 0.5 V, we constructed a hybrid electrolytic water system with coupled hydrogen evolution reaction (HER) and formaldehyde oxidation reaction (FOR). For FOR, the abundant Cu0 and Cu+ in nitrogen-doped Cu/Cu2+1O on Cu foam (N-Cu/Cu2+1O/CF) can effectively promote the adsorption and activation of H2O and HCHO molecules, and facilitate the cleavage of O-H and C-H, while nitrogen doping can promote the exposure of Cu active sites. For HER//FOR, a cell voltage of only 0.42 V is required to achieve 500 mA cm−2. The system can not only produce H2 routinely at the cathode through HER but also release H2 by HCHO oxidation. The construction of a dual hydrogen production system with industrial current density at ultra-low voltage provides a new idea to reduce the cost of hydrogen production.