Metal-based Electrocatalysts Research Articles

Electrospun Micro/Nanofiber-Based Electrocatalysts for Hydrogen Evolution Reaction: A Review

Hydrogen is regarded as an ideal energy carrier to cope with the energy crisis and environmental problems due to its high energy density, cleanliness, and renewability. Although there are several primary methods of industrial hydrogen production, hydrogen evolution reaction (HER) is an efficient, eco-friendly, and sustainably green method for the preparation of hydrogen which has attracted considerable attention. However, this technique is characterized by slow reaction kinetics and high energy potential owing to lack of electrocatalysts with cost-effective and high performance which impedes its scale-up. To address this issue, various studies have focused on electrospun micro/nanofiber-based electrocatalysts for HER due to their excellent electron and mass transport, high specific surface area, as well as high porosity and flexibility. To further advance their development, recent progress of highly efficient HER electrospun electrocatalysts is reviewed. Initially, the characteristics of potential high-performance electrocatalysts for HER are elucidated. Subsequently, the advantages of utilizing electrospinning technology for the preparation of electrocatalysts are summarized. Then, the classification of electrospun micro/nanofiber-based electrocatalysts for HER are analyzed, including metal-based electrospun electrocatalyst (noble metals and alloys, transition metals, and alloys), metal–non-metal electrocatalysts (metal sulfide-based electrocatalysts, metal oxide-based electrocatalysts, metal phosphide-based electrocatalysts, metal nitride-based electrocatalysts, and metal carbide-based electrocatalysts), metal-free electrospun micro/nanofiber-based electrocatalysts, and hybrid electrospun micro/nanofiber-based electrocatalysts. Following this, enhancement strategies for electrospun micro/nanofiber-based electrocatalysts are discussed. Finally, current challenges and the future research directions of electrospun micro/nanofiber-based electrocatalysts for HER are concluded.

Visualizing the Structure and Dynamics of Transition Metal-Based Electrocatalysts Using Synchrotron X-Ray Absorption Spectroscopy.

As the global energy structure evolves and clean energy technologies advance, electrocatalysis has become a focal point as a critical conversion pathway in the new energy sector. Transitional metal electrocatalysts (TMEs) with their distinctive electronic structures and redox properties show great potential in electrocatalytic reactions. However, complex reaction mechanisms and kinetic limitations hinder the improvement of energy conversion efficiency, highlighting the necessity for comprehensive studies on structure and performance of electrocatalysts. X-ray Absorption Fine Structure (XAFS) spectra stand out as a robust tool for examining the electrocatalyst's structures and performance due to its atomic selectivity and sensitivity to local environments. This review delves into the application of XAFS technology in characterizing TMEs, providing in-depth analyses of X-ray Absorption Near-Edge Structure (XANES) spectra, and Extended XAFS (EXAFS) spectra in both R-space and k-space. These analyses reveal intrinsic structural information, electronic interactions, catalyst stability, and aggregation morphology. Furthermore, the paper examines advancements in in-situ XAFS techniques for real-time monitoring of active site changes, capturing critical intermediate and transitional states, and elucidating the evolution of active species during electrocatalytic reactions. These insights deepen our understanding on structure-activity relationship of electrocatalysts and offer valuable guidance for designing and developing highly active and stable electrocatalysts.

Iron-Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation.

The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non-noble metal-based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three-dimensional (3D) nanoflower-like electrocatalyst (CFMO) via a simple one-step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O-O radical coupling for enhanced O2 evolution. The optimized CFMO-2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm-2, alongside exceptional long-term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal-based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO-2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm-2. In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First-principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non-noble metal-based electrocatalysts and the development of AEMWE.

Exploring Two-Dimensional MOF-Derived Co/Ni Species for Efficient Electrocatalytic Hydrogen Evolution Reaction

Hydrogen evolution reaction (HER) has received a lot of attention due to its promising advantages in producing “green hydrogen” via electrocatalysis with low cost and high efficiency. Until now, developing transition metal-based electrocatalysts for HER has been a great challenge. In this regard, we reported a facile strategy to fabricate Co/Ni species encapsulated by carbon structure (CoNi@C) through annealing two-dimensional (2D) metal-organic framework (MOF) nanosheets. The CoNi@C that was prepared under 600 °C achieved the highest catalytic performance in 1.0 M KOH electrolyte with an overpotential of 330 mV to acquire 100 mA cm−2. In addition, the effect of KOH concentrations on the HER performance of CoNi@C-600 was explored. In 3.0 M KOH electrolyte, the current density of 100 mA cm−2 has been attained at a bias potential of 80 mV. The alkaline environment can improve the electrocatalytic performance and further enhance the stability of the as-prepared catalysts. This work would endow promising opportunities for manipulating MOF-based structures through pyrolysis to fabricate highly efficient electrocatalysts.

Na-doped cobalt spinel electrocatalysts prepared by programmed electrostatic spraying for improving OER activity and durability in acidic media

The daunting challenge to establish a trade-off among the activity, durability, and cost of electrocatalysts for oxygen evolution reaction (OER) with sluggish reaction kinetics impedes the practical green energy conversion. Hereby, a non-noble metal-based electrocatalyst (i.e., Na-doped Co3O4) was in-situ prepared by programmed electrostatic spraying as an advanced alternative to the costly and scarce state-of-the-art IrO2 and RuO2-based electrocatalysts. The utilization of this sprayer facilitates intimate contact with the substrate electrode and provides short ion diffusion paths, facilitating efficient electron transport. Additionally, the doping of Na ions into the Co3O4 structure results in structural distortion and charge redistribution, leading to the generation of oxygen vacancies (OVs). These OVs enhance the activity of lattice oxygen atoms, thus enabling rapid and durable oxygen evolution in an acidic media (0.5 M H2SO4). The optimal Na-Co3O4 (AA) exhibits a notably low overpotential of 360 mV@10 mA·cm−2 and at least 200 h stability. In addition, density functional theory (DFT) calculations confirm that the incorporation of Na ions significantly elevates electrical conductivity by decreasing the energy band gap and reduces the free energy barrier for the conversion of *O to *OOH, thereby improving the intrinsic OER activity. Finally, by implanting the catalyst in a single-cell proton exchange membrane water electrolyzer (PEMWE), the current density of 100 mA·cm−2 is achieved at a voltage of 1.62 V. This innovative non-noble metal catalyst holds great potential for scalable PEMWE anodes.

Electrocatalytic CO2 reduction to HCO2H by protic NHC-Ir complexes

In electrochemical CO2-conversion strategies, various transition metal-based molecular electrocatalysts are employed to reduce CO2 into products like CO and HCO2H, with H2 as a competitive side product. However, achieving selectivity towards HCO2H remains challenging, and suitable catalysts for the same are limited. Herein we report a normal and an abnormal protic-NHC-based Cp*Ir(III)-half sandwich complexes for catalytic CO2 electroreduction in an aqueous acetonitrile solvent. Both the catalysts predominantly produced HCO2H as the CO2-reduced product at an applied potential of –2.66 V vs Fc+/Fc with 5 % H2O as the proton source; however, the normal protic-NHC-bound complex achieved a Faradic efficiency (FE) of 86±4 %, while the complex with the abnormal protic-NHC ligand furnished FE up to 72±4 %. The protic proton of the protic NHC ligand in these complexes was proposed to participate in a proton relay process, facilitating generation of the crucial Ir–H intermediate, which reacts with CO2 to produce HCO2H through stabilization of the Ir–OCHO intermediate.

Structural Regulation of a Multi-Component Co2P2O7-MoN/NC Electrocatalyst for Efficient Oxygen Evolution Reaction.

Realizing efficient and durable non-precious metal-based electrocatalysts for oxygen evolution reaction (OER) still remains a great challenge. Here, a multi-component composite of Co2P2O7-MoN/NC containing pyrophosphate, nitride, and nitrogen-doped carbon is successfully prepared via a facile two-step synthesis method. Combining the structural regulation between the active metal- and non-metal-based species, Co2P2O7-MoN/NC demonstrates superior activity and durability for OER, requiring an overpotential of 278 mV at a current density of 10 mA cm-2, a Tafel slope of 83.3 mV dec-1, and long-term stability over 100 h in an alkaline solution. Post-characterizations reveal that synergistic effect among stable Co2P2O7, partially dissolved MoN, N-doped carbon, and new-formed CoOOH nanosheets enable structural reconstruction, fast charge transfer, and formation of oxygen-containing intermediates, promoting the OER performance significantly. This work provides a promising pathway to tune multi-components to fabricate efficient transition-metal-based electrocatalysts in energy conversion applications.

Innovative Air Cathode with Ni-Doped Cobalt Sulfide in Highly Ordered Macroporous Carbon Matrix for Rechargeable Zn-Air Battery.

To realize the practical application of rechargeable Zn-Air batteries (ZABs), it is imperative to develop a non-noble metal-based electrocatalyst with high electrochemical performance for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, Ni-doped Co9S8 nanoparticles dispersed on an inverse opal-structured N, S co-doped carbon matrix (IO─NixCo9-xS8@NSC) as a bifunctional electrocatalyst is presented. The unique 3D porous structure, arranged in an inverse opal pattern, provides a large active surface area. Also, the conductive carbon substrate ensures the homogeneous dispersion of NixCo9-xS8 nanocrystals, preventing aggregation and increasing the exposure of active sites. The introduction of heteroatom dopants into the Co9S8 structure generates defect sites and enhances surface polarity, thereby improving electrocatalytic performance in alkaline solutions. Consequently, the IO─NixCo9-xS8@NSC shows excellent bifunctional activity with a high half-wave potential of 0.926V for ORR and a low overpotential of 289mV at 10mA cm-2 for OER. Moreover, the rechargeable ZAB assembled with prepared electrocatalyst exhibits a higher specific capacity (768 mAh gZn -1), peak power density (180.2mW cm-2), and outstanding stability (over 160h) compared to precious metal-based electrocatalyst.

Advanced multi-component FeCoCuAlMo intermetallic electrocatalysts for efficient and sustainable hydrogen evolution in alkaline freshwater and seawater

Electrolyzing seawater to produce hydrogen is a promising sustainable energy production technology. The current non-precious metal-based hydrogen evolution reaction (HER) electrocatalysts demonstrate inadequate catalytic activity and poor stability in seawater electrolyte. Therefore, developing stable and efficient non-precious metal-based HER electrocatalysts is a major challenge for achieving sustainable green energy development. This work reports a multi-component intermetallic catalyst FeCoCuAlMo prepared by arc melting and chemical dealloying methods. The electrocatalytic hydrogen evolution performance of catalysts with varying atomic ratios (FeCoCu)20(Al70Mo30)80, (FeCoCu)30(Al70Mo30)70, (FeCoCu)40(Al70Mo30)60, and (FeCoCu)50(Al70Mo30)50 in alkaline seawater and alkaline electrolyte was studied. The findings indicate that these catalysts primarily consist of AlMo3 and (Cu0.35Fe0.35Co0.3)Al, among which the dealloyed (FeCoCu)30(Al70Mo30)70 exhibits excellent catalytic activity with overpotentials of 137.54 and 116.91 mV at a current density of 100 mA/cm2 in alkaline seawater and alkaline electrolyte, respectively, outperforming most catalysts. Additionally, it demonstrated long-term stability in alkaline seawater and alkaline electrolyte for 250 and 400 h without significant decay at overpotentials of 236 mV and 276 mV, respectively. This improved performance can be attributed to the unique structure of the multi-component intermetallic compound, which provides good thermodynamic stability and synergistic effects among its constituents, thereby enhancing HER performance. Within this multi-component intermetallic compound, AlMo3 particles serve as the primary conductive medium to accelerate electron transfer, while (Cu0.35Fe0.35Co0.3)Al serves as the main active site, resulting in a stable structure that provides the catalyst with high catalytic activity and good stability. Thus, the (FeCoCu)30(Al70Mo30)70 electrocatalyst is a promising candidate for seawater electrolysis aimed at hydrogen production.

Oxygen-coordinated cobalt single atom steered by doped-O and CoO for efficient hydrogen evolution at industrial current densities

The exploration and design of highly active, low-cost, transition metal-based electrocatalysts are crucial for large-scale green hydrogen production. Here, the heterostructure of oxygen-coordinated cobalt single atoms with O-doped carbon and CoO nanowires (Co-O-C-O/CoO/CF) is constructed for efficient and stable HER at industrial current densities. Benefiting from the synergistic effect of O doping and CoO nanowires, Co-O-C-O/CoO/CF exhibits extremely low overpotentials of 24.8, 229, and 239 mV to achieve current densities of 10, 500, and 1000 mA cm−2 in 1.0 M KOH solution, respectively, and operates stably for 1000 h at 1000 mA cm−2. Additionally, when coupled with NiFe-LDH in a self-assembled electrolyzer, it delivers a high current density of 1000 mA cm−2 at 1.97 V, along with outstanding stability, outperforming Pt/C||NiFe-LDH and most reported electrolyzers. Density functional theory (DFT) calculations reveal that the optimized d-band center and binding strength of H* and OH* intermediates for Co-O-C-O/CoO/CF lower the energy barrier of the rate-determining step. This work provides a new pathway for engineering Co-based catalysts for green hydrogen production at industrial current densities.

Iron, cobalt embedded nitrogen-doped carbon derived from conjugated macrocyclic polymers as electrocatalysts for oxygen reduction reaction

The synthesis of earth-abundant metal-based electrocatalysts for deploying electrochemical energy devices has become an area of considerable interest. Herein, we have illustrated a facile Friedel-Crafts reaction for designing a metalloporphyrin polymer followed by its calcination to synthesize cauliflower-like nitrogen-doped iron-cobalt bimetallic electrocatalyst (FeCoTpp-900-2) and its satisfactory performance toward reducing oxygen. The bimetallic FeCoTpp-900-2 catalyst exhibits a half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE)) and an onset potential (Eonset) of 0.95 V (vs. RHE). The notable electrocatalytic activity for oxygen reduction reaction (ORR) of FeCoTpp-900-2 is attributed to the presence of ORR active nitrogen species along with the Fe-Nx/Co-Nx sites. In addition, FeCoTpp-900-2 possesses an appreciable amount of mesopores responsible for the ORR behavior. Notably, the zinc-air battery consisting of FeCoTpp-900-2 as the catalyst for the air cathode presents a maximal power density of 127.53 mW cm−2 and robust durability for 24 hours (h). Therefore, this work can contribute to the facile synthesis of bimetallic electrocatalysts with non-noble metals to explore their applications in ORR.

Electrodeposition of Ni–MoS2 as effective hydrogen evolution reaction catalysts in alkaline media

Highly active, long-lasting, and economically feasible nonprecious metal-based electrocatalysts are urgently required for the slow hydrogen evolution reaction (HER) in alkaline conditions. Direct current (DC) electrodeposition was used to develop the highly active Ni–MoS2 composite coatings for efficient hydrogen generation. Scanning electron microscopy (SEM), Energy Dispersive X Ray Spectroscopy (EDS), X-ray diffraction (XRD), and linear sweep voltammetry (LSV) were used to evaluate the coatings. Ni–MoS2 composite coatings behaved almost identically to pure platinum metal. The Ni–MoS2 coating produced 1.0 g/l demonstrated a low overpotential for HER. The HER process's analyzed from Volmer-Tafel mechanistic route has an extremely low slope of 56.5 mV/dec. All the coated samples were subjected to chronopotentiometry (CP). This catalyst's high HER performance shows that it has significant potential for practical applications.

Multilayer Porous Fe/Co-N-MWCNT Electrocatalyst For Rechargeable Zinc-Air Batteries.

The design of efficient, stable, low-cost non-precious metal-based electrocatalysts with enhanced oxygen reduction reaction (ORR) activity has garnered significant attention in the scientific community. This study introduces a novel electrocatalyst, Fe/Co-N-MWCNT, synthesized through the in-situ growth of ZIF-8 and Fe/Co-Phen on multi-walled carbon nanotubes (MWCNTs), followed by pyrolysis at varying temperatures to optimize its properties. The inclusion of Fe and Co during the pyrolysis process facilitated the creation of metal active sites and Fe-Co, enhancing electron transfer and ORR activity. Compared to Pt/C (E1/2=0.854 V, JL=4.90 mA cm-2), Fe/Co-N-MWCNT exhibited a similar half-wave potential (E1/2=0.812 V) and an improved limiting current density (JL=5.37 mA cm-2). Moreover, Fe/Co-N-MWCNT displayed remarkable stability, showing only a 7 mV negative shift in E1/2 after 2000 cycles. Ampere response testing indicated a current decay of only 7.8 % for Fe/Co-N-MWCNT after 10000 s, while Pt/C experienced a decay of about 18.4 %. The exceptional catalytic stability of Fe/Co-N-MWCNT positions it as a promising candidate for rechargeable zinc-air batteries, attributed to its high pyridinic nitrogen content, unique structure, and abundant metal active sites.

Construction of a Three-Phase MnS2/Co4S3/Ni3S2 Heterostructure for Boosting Oxygen Evolution.

The rational construction of highly efficient electrocatalysts for the oxygen evolution reaction (OER) plays a critical role in energy conversion systems. Designing heterostructures is a common and effective strategy to improve the performance of electrocatalysts. In this paper, an MnS2/Co4S3/Ni3S2 heterostructure was synthesized on Ni foam using a one-step vulcanization method. It provides a modified electronic structure and plentiful three-phase heterogeneous interfaces that can effectively enrich the active sites and accelerate electron transfer, thereby improving the OER activity. Thanks to the heterostructure, the MnS2/Co4S3/Ni3S2 exhibits a low overpotential of 265 and 304 mV for the OER to reach current densities of 50 and 100 mA/cm2, respectively. Furthermore, the surface reconstruction of MnS2/Co4S3/Ni3S2 has been investigated, which revealed the formation of metal hydr(oxy)oxides evolved during the OER process. This work provides a facile strategy for constructing three-phase heterostructures, shedding light on the development of high-performance, nonprecious metal-based OER electrocatalysts.

Enhanced oxygen evolution on A-site defect perovskite oxide through interfacial engineering

Perovskite oxides are emerging as promising alternative to precious metal-based electrocatalysts for oxygen evolution reactions. Despite their potential, their catalytic activity is often insufficient for practical applications. In this study, we demonstrate that introducing A-site defects in LaNiO3 perovskite oxides promotes B-site exsolution during the reduction process. Subsequent chemical vapor deposition introduces selenium, forming an electrocatalyst with a heterojunction structure. Comprehensive characterization and electrochemical testing reveal that the r-La0.9NiO3/NiSex heterojunction structure, resulting from B-site exsolution induced by A-site defects, significantly enhances the electrocatalytic performance of the La0.9NiO3 electrocatalyst. This novel structure not only increases oxygen vacancy concentration but also improves the wettability of the electrocatalyst, as indicated by a reduced bubble contact angle in water. These modifications lead to a notable improvement in the electrochemical performance of the r-La0.9NiO3/NiSex electrocatalyst. At a current density of 10 mA·cm−2, the electrocatalyst exhibits an overpotential of 297.6 mV, with substantially increased mass activity. This study presents a novel approach to catalyst design in electrocatalysis, leveraging A-site defect induced B-site exsolution in perovskite oxides. The strategy of reduction followed by doping offers a robust framework for developing more efficient electrocatalysts, paving the way for advancements in the field of heterogeneous catalysis.

Promoting Electrocatalytic Reduction of CO2 and Nitrate to Urea on N-Doped Porous Hollow Carbon Spheres.

The electrocatalytic coreduction of CO2 and nitrate is a green method for urea synthesis, mitigating CO2 emission and nitrate contamination. However, its slow kinetics and high energy barrier result in a poor urea production performance. Herein, we reported N-doped porous hollow carbon spheres (N-PHCS) for promoting CO2 and nitrate conversion to urea via nanoconfinement and N-doping from both reaction kinetics and thermodynamics. A high urea yield of 12.0 mmol h-1 gcat-1 with Faradaic efficiency of 19.1% was achieved on N-PHCS at -1.0 V (vs Ag/AgCl), which was comparable to or even higher than those of metal-based electrocatalysts reported. The experimental and theoretical calculation results revealed that carbon spheres with an appropriate interior void and pore size were favorable for confining reactants and intermediates to accelerate urea production, while N-doping can reduce the energy barrier for urea synthesis. By regulating the microstructure and N doping of N-PHCS, it showed a superior performance for urea electrosynthesis. The energy favorable pathway for urea synthesis was through the C-N coupling reaction of *NO and *CO, and pyridinic N can reduce the reaction energy barrier.

Reductive Inner-Sphere Electrosynthesis of Ammonia via a Nonelectrocatalytic Outer-Sphere Redox.

Electrochemistry of outer-sphere redox molecules involves an essentially intact primary coordination sphere with minimal secondary sphere adjustments, resulting in very fast electron transfer events even without a noble metal-based electrocatalyst. Departing from conventional electrocatalytic paradigms, we incorporate these minimal reaction coordinate adjustments of outer-sphere species to stimulate the electrocatalysis of energetically challenging inner-sphere substrates. Through this approach, we are able to show an intricate 8e- and 9H+ transfer inner-sphere reductive electrocatalysis at almost half the energy input of a conventional inner-sphere electron donor. This methodology of employing outer-sphere redox species has the potential to notably improve the cost and energy benefits in electrochemical transformations involving fundamental substrates such as water, CO2, N2, and many more.

Ligand-Hybridization Activates Lattice-Hydroxyl-Groups of NiCo(OH)x Nanowires for Efficient Electrosynthesis.

Electrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high-valence metal active sites toward 5-hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value-added chemical of 2,5-furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand-hybridized NiCo(OH)x nanowires (BZ-NiCo(OH)x) with ample electron-deficient Ni/Co sites for HMFOR. The robust electron-withdrawing capability of benzoic acid ligands in BZ-NiCo(OH)x speeds up the electrochemical activation and dehydrogenation of lattice-hydroxyl-groups (M2+-O-H⇌M3+-O), boosting the formation of abundant electron-deficient and high-valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ-NiCo(OH)x delivers a remarkable current density of 111.20 mA cm-2 at 1.4 V for HMFOR, exceeding that of NiCo(OH)x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand-hybridized strategy in this work introduces a novel perspective for designing high-performance transition metal-based electrocatalysts for biomass conversion.

Microwave-edge-thermal effect induced growth of coral-like self-supporting CoFe2O4/NF electrocatalysts for efficient water splitting at high-current–density

High-efficiency and long-term water-splitting to produce hydrogen under the high-current–density (HCD) environment is a severe challenge because the swift-consumption of electrolyte and large-production of bubbles require better charge/mass-transfer capability and durability of electrocatalysts. Rationally design and effectively construct of three-dimensional (3D) hierarchical electrocatalysts is the promising solutions to accelerate the charge/mass transfer rates during water splitting process. Herein, a 3D self-supporting coral-like oxygen evolution reaction (OER) electrode was synthesized using a microwave-edge-thermal (MET) effect induced heterogeneous-nucleation/oriented-attachment growth process by in-situ growing CoFe2O4 nanocrystals on nickel-foams (CoFe2O4/NF). SEM, TEM, electrolyte/catalyst contact angles, in-situ observation of O2 bubbles generation-evolution process, and three-electrode configuration (TEC) and anion-exchange-membrane (AEM) electrocatalytic OER tests at the HCD were used to investigated the structure–activity relationship of the CoFe2O4/NF electrode. The CoFe2O4/NF electrode offered super hydrophilic/aerophobic surfaces and firmly bonded interfaces, resulting in quicker charge/mass-transfer rates and long-term durability under the HCD conditions. The typical electrode exhibited a low OER overpotential of 0.24 V at 10 mA cm−2 and a Tafel slope of 35.2 mV dec−1; its alkaline AEM electrolyzer (Pt || CoFe2O4/NF) yielded a HCD of 1200 mA cm−2 at only 2.36 V and 60˚C and kept stable over 120 h. This work provides a new insight into the design and fabrication of active and stable non-noble metal-based OER electrocatalysts for cost-effective water-electrolysis applications.

Surface active sites and interphase engineering into metal oxide hydrates enabled by ions substitution for efficient water splitting

The expanding requirement of energy-effective and cost-efficient water electrolysis has prompted studies of earth-abundant metal-based electrocatalysts. In this study, we study the typical substitution strategies of cation (Pt) or anion (Se) for modifying surface active sites or interphase engineering to tune electronic structure of bimetallic nickel molybdenum oxide hydrates (NiMoO4·xH2O), thus effectively improving catalytic properties toward hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). Result of the cation substitution achieves PtSA–NiMoO4·xH2O catalyst with abundant doped Pt single atoms on surface, which promotes high HER activity with a small overpotential of 73 mV at a current yield of 10 mA cm−2 in alkaline medium. Meanwhile, Se–NiMoO4·xH2O catalyst, an outcome of the anion substitution approach, has unique interfaces of NiSe-NiMoO4 heterostructure and thus exhibits a desired overpotential of only 297 mV for OER. The combination of PtSA–NiMoO4·xH2O(–)//Se–NiMoO4·xH2O(+) couple results in a two-electrode electrolyzer cell, which requires a small cell voltage of 1.48, 1.54 and 1.59 V to deliver a response of 10 mA·cm−2 at 75, 50 and 25 °C, respectively, along with negligible performance decay during 50 h operation. These results highlight the potential of our catalyst engineering strategies to achieve high-performance green hydrogen production.