Modulating the Energy Barrier via the Synergism of Cu3P and CoP to Accelerate Kinetics for Bolstering Oxygen Electrocatalysis in Zn-Air Batteries.

Modulating the energy barrier of reaction intermediates to surmount sluggish kinetics is an utterly intriguing strategy for amplifying the oxygen reduction reaction. Herein, a Cu3P/CoP hybrid is incorporated on hollow porous N-doped carbon nanospheres via dopamine self-polymerization and high-temperature treatment. The resultant Cu3P/CoP@NC showcases a favorable mass activity of 4.41 mA mg-1 and a kinetic current density of 2.38 mA cm-2. Strikingly, the catalyst endows the aqueous Zn-air battery (ZAB) with a large power density of 209.0 mW cm-2, superb cyclability over 317 h, and promising application prospects in flexible ZAB. Theoretical simulations reveal that Cu functions as a modulator to modify the free energy of intermediates and adsorbs the O2 on the Co sites, hence rushing the reaction kinetics. The open and hydrophilic hollow spherical mesoporous structure provides unimpeded channels for reactant diffusion and electrolyte penetration, whereas the exposed inner and outer surfaces can confer a plethora of accessible actives sites. This research establishes a feasible design concept to tune catalytic activity for non-noble metal materials by construction of a rational nanoframework.

Fine-tuning nanoflower-like Fe/Co hybrids with high content oxyhydroxide accelerating oxygen evolution kinetics.

Iron hydroxide (FeOOH) is a potential active component in iron-based electrocatalysts for water electrolysis. However, its catalytic performance is constrained by its slow oxygen evolution reaction (OER) kinetics. Herein, we synthesized a nanoflower-like FeCo-hydro(oxy)oxides composite with tunable Fe/Co ratios (Fex-Coy) on nickel foam (NF) via a one-step electrodeposition technique. This method allows for precise control over the morphology and composition of the hybrid nanoflowers. The optimized Fe9-Co1 discloses favorable OER performance with a low overpotential of 222 mV at 50 mA cm-2 and demonstrates good stability exceeding 60 h at 10 mA cm-2. Further, an assembled Fe9-Co1(+)||Pt/C(-) dual-electrode configuration achieves a low cell voltage of 1.73 V at the current density of 100 mA cm-2 for water splitting, with long-term stability for 70 h and minimal degradation. Studies indicate that the distinctive nanoflower morphology of Fe9-Co1 enhances active site exposure, while both FeOOH and reconstructed CoOOH serve as catalytic centers, contributing to the observed OER performance. This work introduces a facile approach for synthesizing OER electrocatalysts, underscoring the role of the high-valence state of Fe/Co as active sites in the OER process.

Real Active Site Identification of Co/Co3O4 Anchoring Ni-MOF Nanosheets with Fast OER Kinetics for Overall Water Splitting.

Doping metals and constructing heterostructures are pivotal strategies to enhance the electrocatalytic activity of metal-organic frameworks (MOFs). Nevertheless, effectively designing MOF-based catalysts that incorporate both doping and multiphase interfaces poses a significant challenge. In this study, a one-step Co-doped and Co3O4-modified Ni-MOF catalyst (named Ni NDC-Co/CP) with a thickness of approximately 5.0 nm was synthesized by a solvothermal-assisted etching growth strategy. Studies indicate that the formation of the Co-O-Ni-O-Co bond in Ni NDC-Co/CP was found to facilitate charge density redistribution more effectively than the Co-O-Ni bimetallic synergistic effect in NiCo NDC/CP. The designating Ni NDC-Co/CP achieved superior oxygen evolution reaction (OER) activity (245 mV @ 10 mA cm-2) and robust long stability (100 h @ 100 mA cm-2) in 1.0 M KOH. Furthermore, the Ni NDC-Co/CP(+)||Pt/C/CP(-) displays pregnant overall water splitting performance, achieving a current density of 10 mA cm-2 at an ultralow voltage of 1.52 V, which is significantly lower than that of commercial electrolyzer using Pt/C and IrO2 electrode materials. In situ Raman spectroscopy elucidated the transformation of Ni NDC-Co to Ni(Co)OOH under an electric field. This study introduces a novel approach for the rational design of MOF-based OER electrocatalysts.

Self-etching assembly of designed NiFeMOF nanosheet arrays as high-efficient oxygen evolution electrocatalyst for water splitting.

2D metal-organic frameworks (MOFs) have emerged as potential candidates for electrocatalytic oxygen evolution reactions (OER) due to their inherent properties like abundant coordination unsaturated active sites and efficient charge transfer. Herein, a versatile and massively synthesizable self-etching assembly strategy wherein nickel-iron foam (NFF) acts as a substrate and a metal ion source. Specifically, by etching the nickel-iron foam (NFF) surface using ligands and solvents, Ni/Fe metal ions are activated and subsequently reacted under hydrothermal conditions, resulting in the formation of self-supporting nanosheet arrays, eliminating the need for external metal salts. The obtained 33 % NiFeMOF/NFF exhibits remarkable OER performance with ultra-low overpotentials of 188/231 mV at 10/100 mA cm-2, respectively, outperforming most recently reported catalysts. Besides, the built 33 % NiFeMOF/NFF(+)||Pt/C(-) electrolyzer presents low cell voltages of 1.55/1.83 V at 10/100 mA cm-2, superior to the benchmark RuO2 (+)||Pt/C(-), implying good industrialization prospects. The excellent catalytic activity stems from the modulation of the electronic spin state of the Ni active site by the introduction of Fe, which facilitates the adsorption process of oxygen-containing intermediates and thus enhances the OER activity. This innovative approach offers a promising pathway for commercial-scale sustainable energy solutions.

Highly Active and Robust Catalyst: Co2B-Fe2B Heterostructural Nanosheets with Abundant Defects for Hydrogen Production.

A high-performance and reusable nonnoble metal catalyst for catalyzing sodium borohydride (NaBH4) hydrolysis to generate H2 is heralded as a nuclear material for the fast-growing hydrogen economy. Boron vacancy serves as a flexible defect site that can effectively regulate the catalytic hydrolysis performance. Herein, we construct a uniformly dispersed and boron vacancy-rich nonnoble metal Co2B-Fe2B catalyst via the hard template method. The optimized Co2B-Fe2B exhibits superior performance toward NaBH4 hydrolysis, with a high hydrogen generation rate (5315.8 mL min-1 gcatalyst-1), relatively low activation energy (35.4 kJ mol-1), and remarkable cycling stability, outperforming the majority of reported catalysts. Studies have shown that electron transfer from Fe2B to Co2B, as well as abundant boron defects, can effectively modulate the charge carrier concentration of Co2B-Fe2B catalysts. Density functional theory calculations confirm that the outer electron cloud density of Co2B is higher than that of Fe2B, among which Co2B with high electron cloud density can selectively adsorb BH4- ions, while the electron-deficient Fe2B is favorable for capturing H2O molecules, therefore synergistically promoting the catalytic NaBH4 hydrolysis to produce H2.

Geometric and Electronic Engineering in Co/VN Nanoparticles to Boost Bifunctional Oxygen Electrocatalysis for Aqueous/Flexible Zn-Air Batteries.

Modulating metal-metal and metal-support interactions is one of the potent tools for augmenting catalytic performance. Herein, highly active Co/VN nanoparticles are well dispersed on three-dimensional porous carbon nanofoam (Co/VN@NC) with the assistance of dicyandiamide. Studies certify that the consequential disordered carbon substrate reinforces the confinement of electrons, while the coupling of diverse components optimizes charge redistribution among species. Besides, theoretical analyses confirm that the regulated electron configuration can significantly tune the binding strength between the active sites and intermediates, thus optimizing reaction energy barriers. Therefore, Co/VN@NC exhibits a competitive potential difference (ΔE, 0.65 V) between the half-wave potential of ORR and OER potential at 10 mA cm-2, outperforming Pt/C+RuO2 (0.67 V). Further, catalyst-based aqueous/flexible ZABs present superior performances with peak power densities of 156 and 85 mW cm-2, superior to Pt/C-based counterparts (128 and 73 mW cm-2). This research provides a pivotal foundation for the evolution of bifunctional catalysts in the energy sector.

Oxalic Acid-Assisted Vacancy Engineering Promotes Iron-Copper Sulfide Nanosheets for High-Current Density Water Oxidation.

The effective defect and interface coupling are pivotal for the promotion of the catalytic activity for the oxygen evolution reaction. Herein, we report novel hybrid nanosheets with sulfur vacancies composed of FeS2 and Cu39S28 grown on Cu foam (Vs-FeS2/Cu39S28). The optimal Vs-FeS2/Cu39S28 exhibits a high current output of 500 mA cm-2 at a low overpotential of 370 mV and robust stability for 60 h at 100 mA cm-2, surpassing the values of most previously reported Cu-based catalysts. Furthermore, a two-electrode electrolyzer made by pairing the prepared catalyst with commercial Pt/C requires a low cell voltage of 1.75 V at 100 mA cm-2 and is retained over 80 h. Key to its excellent performance is the synergism between intertwined FeS2 and Cu39S28 domains, enriched by the deliberate introduction of sulfur vacancies, thus optimizing the electronic structure and causing the proliferation of catalytic active sites. This work presents a potent Cu-based electrocatalyst and emphasizes the leveraging of non-precious metals for efficient water oxidation.

Synergistic vacancy engineering of Co/MnO@NC catalyst for superior oxygen reduction reaction in liquid/solid zinc-air batteries.

The pursuit of efficient and economically viable catalysts for liquid/solid-state zinc-air batteries (ZABs) is of paramount importance yet presents formidable challenge. Herein, we synthesized a vacancy-rich cobalt/manganese oxide catalyst (Co/MnO@NC) stabilized on a nitrogen-doped mesoporous carbon (NC) nanosphere matrix by leveraging hydrothermal and high-temperature pyrolysis strategy. The optimized Co/MnO@NC demonstrates fast reaction kinetics and large limiting current densities comparable to commercial Pt/C in alkaline electrolyte for oxygen reduction reaction (ORR). Moreover, the Co/MnO@NC serves as an incredible cathode material for both liquid and flexible solid-state ZABs, delivering impressive peak power densities of 217.7 and 63.3 mW cm-2 and robust long-term stability (459 h), outperforming the state-of-the-art Pt/C and majority of the currently reported catalysts. Research indicates that the superior performance of the Co/MnO@NC catalyst primarily stems from the synergy between the heightened electrical conductivity of metallic Co and the regulatory capacity of MnO on adsorbed oxygen intermediates. In addition, the abundance of vacancies regulates the electronic configuration, and superhydrophilicity facilitates efficient electrolyte diffusion, thereby effectively ensuring optimal contact between the active site and reactants. Besides, the coexisting NC layer avoids the shedding of active sites, resulting in high stability. This work provides a viable approach for designing and advancing high-performance liquid/solid-state ZABs, highlighting the great potential of energy storage technology.

Precise Anchoring of Fe Sites by Regulating Crystallinity of Novel Binuclear Ni-MOF for Revealing Mechanism of Electrocatalytic Oxygen Evolution.

Bimetallic metal-organic framework (BMOF) exhibits better electrocatalytic performance than mono-MOF, but deciphering the precise anchoring of foreign atoms and revealing the underlying mechanisms at the atomic level remains a major challenge. Herein, a novel binuclear NiFe-MOF with precise anchoring of Fe sites is synthesized. The low-crystallinity (LC)-NiFe0.33 -MOF exhibited abundant unsaturated active sites and demonstrated excellent electrocatalytic oxygen evolution reaction (OER) performance. It achieved an ultralow overpotential of 230 mV at 10 mA cm-2 and a Tafel slope of 41 mV dec-1 . Using a combination of modulating crystallinity, X-ray absorption spectroscopy, and theoretical calculations, the accurate metal sequence of BMOF and the synergistic effect of the active sites are identified, revealing that the adjacent active site plays a significant role in regulating the catalytic performance of the endmost active site. The proposed model of BMOF electrocatalysts facilitates the investigation of efficient OER electrocatalysts and the related catalytic mechanisms.

Synergistic Co-N/V-N dual sites in N-doped Co3V2O8 nanosheets: pioneering high-efficiency bifunctional electrolysis for high-current water splitting.

Developing affluent dual-metal active sites bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential to achieve large-scale water electrolysis, whereas still remains challenging. Herein, a novel nitrogen-doped cobalt-vanadium oxide with abundant Co-N and V-N dual active sites supported on nickel foam (N-Co3V2O8@NF) is constructed by a controllable impregnation-thermal nitridation strategy. The staggered nanosheet structure ensures optimal exposure of active sites. More importantly, N doping effectively regulates the electronic structure of the metal centers and induces the formation of Co-N and V-N dual active sites, which is conducive to improving the conductivity and hydrophilicity, thus synergistically enhancing the electrocatalytic efficiency. Consequently, the optimized N-Co3V2O8@NF exhibits prominent HER (63 mV@10 mA cm-2) and OER (256 mV@10 mA cm-2) activities, surpassing most contemporary bifunctional electrocatalysts. In practical application, the assembled N-Co3V2O8@NF(+/-) electrolyzer consistently achieved ultra-low cell voltages of 1.97 and 2.03 V at 500 and 1000 mA cm-2, respectively, superior to the benchmark RuO2@NF(+) || Pt/C@NF(-) and showcasing robust durability. This paves the way for its prospective adoption in industrial water electrolysis applications.

Mn-Doped Zn Metal-Organic Framework-Derived Porous N-Doped Carbon Composite as a High-Performance Nonprecious Electrocatalyst for Oxygen Reduction and Aqueous/Flexible Zinc-Air Batteries.

Developing low-cost, efficient, and stable oxygen reduction reaction (ORR) electrocatalysts is crucial for the commercialization of energy conversion devices such as metal-air batteries. In this study, we report a Mn-doped Zn metal-organic framework-derived porous N-doped carbon composite (30-ZnMn-NC) as a high-performance ORR catalyst. 30-ZnMn-NC exhibits excellent electrocatalytic activity, demonstrating a kinetic current density of 9.58 mA cm-2 (0.8 V) and a half-wave potential of 0.83 V, surpassing the benchmark Pt/C and most of the recently reported non-noble metal-based catalysts. Moreover, the assembled zinc-air battery with 30-ZnMn-NC demonstrates high peak power densities of 207 and 66.3 mW cm-2 in liquid and flexible batteries, respectively, highlighting its potential for practical applications. The excellent electrocatalytic activity of 30-ZnMn-NC is attributed to its unique porous structure, the strong electronic interaction between metal Zn/Mn and adjacent N-doped carbon, as well as the bimetallic Mn/Zn-N active sites, which synergistically promote faster reaction kinetics. This work offers a controllable design strategy for efficient electrocatalysts with porous structures and bimetallic active sites, which can significantly enhance the performance of energy conversion devices.

Synergistic Promotion of Large-Current Water Splitting through Interfacial Engineering of Hierarchically Structured CoP-FeP Nanosheets with Rich P Vacancies.

The development of hydrogen evolution reaction (HER) catalysts with high performance under large current density is still a challenge. Introducing P vacancies in heterostructure is an appealing strategy to enhance HER kinetics. This study investigates a CoP-FeP heterostructure catalyst with abundant P vacancies (Vp-CoP-FeP/NF) on nickel foam (NF), which was prepared using dipping and phosphating treatment. The optimized Vp-CoP-FeP catalyst exerted prominent HER catalytic capability, requiring an ultra-low overpotential (58 mV @ 10 mA cm-2 ) and displaying robust durability (50 h @ 200 mA cm-2 ) in 1.0 M KOH solution. Furthermore, the catalyst demonstrated superior overall water splitting activity as cathode, demanding only cell voltage of 1.76 V at 200 mA cm-2 , outperforming Pt/C/NF(-) || RuO2 /NF(+) . The catalyst's outstanding performance can be attributed to the hierarchical structure of porous nanosheets, abundant P vacancies, and synergistic effect between CoP and FeP components, which promote water dissociation and H* adsorption and desorption, thereby synergically accelerating HER kinetics and enhancing HER activity. This study demonstrates the potential of HER catalysts with phosphorus-rich vacancies that can work under industrial-scale current density, highlighting the importance of developing durable and efficient catalysts for hydrogen production.

Oxygen vacancy engineering of mesoporous Bi-Fe2O3@NC multi-channel microspheres for remarkable oxygen reduction and aqueous/flexible Zn-air batteries.

Designing multi-channel mesoporous structure and introducing oxygen vacancies to synergistically enhance oxygen reduction reaction (ORR) activity is crucial for the practical application of zinc-air batteries (ZABs) in the field of energy storage and conversion. Herein, a novel multi-channel mesoporous Bi-Fe2O3 microsphere with abundant oxygen vacancies supported on nitrogen-doped carbon (denoted as Bi-Fe2O3@NC) is constructed and the designated catalyst demonstrates a higher half-wave potential (0.88 V), large limiting current density (5.8 mA cm-2@0.4 V), and superior stability. Besides, the aqueous ZAB utilizing Bi-Fe2O3@NC cathode achieves a high power density of 198.6 mW cm-2 and maintains exceptional stability for 459 h at 5 mA cm-2, superior to most previously reported catalysts. Furthermore, a solid-state ZAB assembled with Bi-Fe2O3@NC shows a power density of 55.9 mW cm-2, highlighting its potential for flexible ZAB applications. The prominent ORR performance of Bi-Fe2O3@NC can be ascribed to its unique multi-channel mesoporous structure and abundant oxygen vacancies, which increase the exposure of active sites and facilitate efficient electron/mass transport. This work provides valuable insights for the rational design of advanced ORR catalysts for the practical requirements of aqueous/flexible ZABs in energy storage and conversion.

Synergistic Regulation of Pt Clusters on Porous Support by Mo and P for Robust Bifunctional Hydrogen Electrocatalysis.

Developing efficient electrocatalysts toward hydrogen oxidation and evolution reactions (HER/HOR) in alkaline electrolytes is essential for realizing renewable hydrogen technologies. Herein, we demonstrate that the introduction of dual-active species such as Mo and P (Pt/Mo,P@NC) can effectively regulate the surface electronic structure of platinum (Pt) and significantly improve the HOR/HER performance. The optimized Pt/Mo,P@NC exhibits remarkable catalytic activity, achieving a normalized exchange current density of 2.89 mA cm-2 and a mass activity of 2.3 mA µgPt-1, which are approximately 2.2 and 13.5 times higher than those of the state-of-the-art Pt/C catalyst, respectively. Moreover, it performs an impressive HER performance with an overpotential of 23.4 mV at 10 mA cm-2, which is lower than most documented alkaline electrocatalysts. Experimental results reveal that the modifying effect of Mo and P optimizes the adsorption of H and OH on Pt/Mo,P@NC, resulting in an outstanding catalytic performance. This work has significant theoretical and practical significance for developing a novel and highly efficient catalyst for bifunctional hydrogen electrocatalysis.

Interfacial engineering of Co5.47N/Mo5N6 nanosheets with rich active sites synergistically accelerates water dissociation kinetics for Pt-like hydrogen evolution.

The development of highly efficient hydrogen evolution electrocatalysts with platinum-like activity requires precise control of active sites through interface engineering strategies. In this study, a heterostructured Co5.47N/Mo5N6 catalyst (CoMoNx) on carbon cloth (CC) was synthesized using a combination of dip-etching and vapor nitridation methods. The rough nanosheet surface of the catalyst with uniformly distributed elements exposes a large active surface area and provides abundant interface sites that serve as additional active sites. The CoMoNx was found to exhibit exceptional hydrogen evolution reaction (HER) activity with a low overpotential of 44 mV at 10 mA cm-2 and exceptional stability of 100 h in 1.0 M KOH. The CoMoNx(-)||RuO2(+) system requires only 1.81 V cell voltage to reach a current density of 200 mA cm-2, surpassing the majority of previously reported electrolyzers. Density functional theory (DFT) calculations reveal that the strong synergy between Co5.47N and Mo5N6 at the interface can significantly reduce the water dissociation energy barrier, thereby improving the kinetics of hydrogen evolution. Furthermore, the rough nanosheet architecture of the CoMoNx catalyst with abundant interstitial spaces and multi-channels enhances charge transport and reaction intermediate transportation, synergistically improving the performance of the HER for water splitting.

Electronic Modulation and Mechanistic Study of Ru-Decorated Porous Cu-Rich Cuprous Oxide for Robust Alkaline Hydrogen Oxidation and Evolution Reactions.

Rational design of high-efficiency and viable electrocatalysts is essential in overcoming the bottleneck of sluggish alkaline hydrogen oxidation/evolution reaction (HOR/HER) kinetics. In this study, a metal-organic framework-derived strategy for constructing a Pt-free catalyst with Ru clusters anchored on porous Cu-Cu2 O@C is proposed. The designed Ru/Cu-Cu2 O@C exhibits superior HOR performance, with a mass activity of 2.7 mA µ g R u - 1 ${{{\rm \mu }{\rm g}}_{{\rm R}{\rm u}}^{-1}}$ at 50 mV, which is about 24 times higher than that of state-of-the-art Pt/C (0.11 mA µ g P t - 1 ${{{\rm \mu }{\rm g}}_{{\rm P}{\rm t}}^{-1}}$ ). Significantly, Ru/Cu-Cu2 O@C also displays impressive HER performance by generating 26 mV at 10 mA cm-2 , which exceeds the majority of documented Ru-based electrocatalysts. Systematic characterization and density functional theory (DFT) calculations reveal that efficient electron transfer between Ru and Cu species results in an attenuated hydrogen binding energy (HBE) of Ru and an enhanced hydroxy binding energy (OHBE) of Cu2 O, together with an optimized H2 O adsorption energy with Cu2 O as the H2 O*-capturing site, which jointly facilitates HOR and HER kinetics.

Conductivity-enhanced porous N/P co-doped metal-free carbon significantly enhances oxygen reduction kinetics for aqueous/flexible zinc-air batteries.

Heteroatom-doped metal-free carbon catalysts for oxygen reduction reactions have gained significant attention because of their unusual activity and economic cost. Here, a novel N/P co-doped porous carbon catalyst (NPPC) with a high surface area for oxygen reduction reaction (ORR) is constructed by a facile high-temperature calcination method employing ZIF-8 as the precursor and red phosphorus as the phosphorus source. In particular, ZIF-8 is firstly calcined to obtain N-doped carbon (NC) followed by further calcination with red phosphorus to obtain NPPC. Ultraviolet photoelectron spectroscopy (UPS) analysis shows that the ultra-low amount of P doping could significantly decrease the work function from 4.32 to 3.86 eV. The resultant catalyst exhibits a promising electrocatalytic activity with a half-wave potential (E1/2) of 0.87 V and a limiting current density (JL) of 5.15 mA cm-2. Besides, it also shows improved catalytic efficiency and excellent durability with a negligible decay of JL after 2000 CV cycles. Moreover, aqueous and solid-state flexible zinc-air batteries (ZAB) using the catalyst show a promising application potential. This work provides new insight into developing P/N-doped metal-free carbon ORR catalysts.

Bifunctional Ru-Cluster-Decorated Co3 B-Co(OH)2 Hybrid Catalyst Synergistically Promotes NaBH4 Hydrolysis and Water Splitting.

Developing a highly efficient bifunctional catalyst for hydrolysis of metal hydrides and spontaneous hydrogen evolution reaction (HER) is essential for substituting conventional fuels for H2 production. Herein, Ru-cluster-modified Co3 B-Co(OH)2 supported on nickel foam (Ru/Co3 B-Co(OH)2 @NF) is constructed by electroless deposition, calcination and chemical reduction. The catalyst exhibits an excellent hydrogen generation rate (HGR) of 4989 mL min-1 g c a t a l y s t - 1 ${{{\rm g}}_{catalyst}^{-1}}$ and good reusability, superior to most previously reported catalysts. Besides, Ru/Co3 B-Co(OH)2 @NF displays a prominent hydrogen evolution reaction catalytic capability with a low overpotential of 153.0 mV at 100 mA cm-2 (50.5 mV at 10 mA cm-2 ), a small Tafel slope of 40.0 mV dec-1 and long-term stability (100 h@10 mA cm-2 ) in 1.0 M KOH. The excellent catalytic H2 generation capacity benefits from the rapid charge transfer promoted by metallic Co3 B, the synergistic catalytic effect of Co3 B-Co(OH)2 and Ru clusters, and the unique composite structure favorable for solute transport and gas emission.

Fine-tune d-band center of cobalt vanadium oxide nanosheets by N-doping as a robust overall water splitting electrocatalyst.

Developing high-activity, long-durability, and noble metal-free oxygen evolution (OER) and hydrogen evolution (HER) cocatalysts are the bottlenecks for efficient overall water splitting (OWS). Here, novel cobalt vanadium oxides doped by nitrogen were synthesized by nitriding Co2V2O7@NF precursor at 300-450 °C for OER and HER reactions. N-Co2V2O7@NF (350 °C) and N-Co2VO4/VO2@NF (400 °C) show remarkable OER and HER performance with overpotentials of 310 mV and 224 mV at high current density (100 mA cm-2). Besides, they also revealed long-term solid stability even after 170 h and 700 h of continuous performance. Furthermore, the N-Co2V2O7@NF(+)||N-Co2VO4/VO2@NF(-) OWS device possesses a cell voltage of 1.93 V at 500 mA cm-2 better than RuO2@NF(+)||Pt/C@NF(-) (2.02 V) and can operate for 60 h with almost no degradation. This extraordinary performance can be attributed to the nanosheet structure, which can maximize the exposure of active sites and accelerate the mass transfer. Moreover, density functional theory (DFT) calculations suggest that N-doping can fine-tune the d-band center and band gap to facilitate intermediate adsorption and electron motion. The method presented here can be applied in other novel N-doped electrocatalysts for the energy field.

Improving the Electrocatalytic Activity of a Nickel-Organic Framework toward the Oxygen Evolution Reaction through Vanadium Doping.

Metal-organic frameworks (MOFs) have been considered as potential oxygen evolution reaction (OER) electrocatalysts owning to their ultra-thin structure, adjustable composition, high surface area, and high porosity. Here, we designed and fabricated a vanadium-doped nickel organic framework (V1-x -Nix MOF) system by using a facile two-step solvothermal method on nickel foam (NF). The doping of vanadium remarkably elevates the OER activity of V1-x -Nix MOF, thus demonstrating better performance than the corresponding single metallic Ni-MOF, NiV-MOF and RuO2 catalysts at high current density (>400 mA cm-2 ). V0.09 -Ni0.91 MOF/NF provides a low overpotential of 235 mV and a small Tafel slope of 30.3 mV dec-1 at a current density of 10 mA cm-2 . More importantly, a water-splitting device assembled with Pt/C/NF and V0.09 -Ni0.91 MOF/NF as cathode and anode yielded a cell voltage of 1.96 V@1000 mA cm-2 , thereby outperforming the-state-of-the-art RuO2 (+) ||Pt/C(-) . Our work sheds new insight on preparing stable, efficient OER electrocatalysts and a promising method for designing various MOF-based materials.