Electrocatalytic Performance For Oxygen Evolution Reaction Research Articles

Enhancing Oxygen Evolution Reaction Performance of Metal-Organic Frameworks through Cathode Activation.

Due to their abundant active sites and porous structures, metal-organic frameworks (MOFs) have garnered significant interest as oxygen evolution reaction (OER) electrocatalysts. Nevertheless, the development of MOF-based electrocatalysts with efficient OER activity and excellent stability simultaneously still faces challenges. Herein, a cathodic activation strategy was used to enhance the OER electrocatalytic performance of M-HHTP for the first time, where M refers to Ni, Cu, Co, Fe, while HHTP denotes 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene. As a prototype, the activated Ni-HHTP (HA-Ni-HHTP) demonstrates outstanding OER performance, with an overpotential as low as 140 mV at 20 mA cm-2 and a small Tafel slope of 78.7 mV-1, surpassing commercial RuO2 and rivaling state-of-the-art MOFs-based electrocatalysts. Characterizations and density functional theory calculations reveal that the superior performance of HA-Ni-HHTP is primarily ascribed to changes in semiconductor type, contact angle, and oxygen vacancy content induced by cathodic activation. Electrochemical impedance spectroscopy analysis using the transmission line model confirms that cathodic activation accelerates charge transport, enhancing the OER process. Furthermore, the cathodic activation strategy holds promise for improving the water oxidation performance of other MOFs such as Fe-HHTP, Co-HHTP, and Cu-HHTP.

Facile top-down fabrication of integrated amorphous NiFe-based electrocatalytic electrodes for high current and long-life oxygen evolution

Developing an industrially relevant electrode with high catalytic activity, stability, and tunable composition/size for large-scale water electrolysis is a significant challenge. We have created an integrated electrode (NFM30-N) for the oxygen evolution reaction (OER) using a facile top-down approach that combines arc melting with dealloying-oxidation. Due to the dealloying-oxidation effect, the as-derived porous amorphous M–O, M–OH, and M–OOH (M = Ni, Fe) nanocones cover the basic NiFeMn alloy. This integrated design enables NFM30-N to exhibit outstanding OER performance at high current densities, requiring low overpotentials of only 282 and 323 mV to achieve large current densities of 100 and 500 mA cm−2, respectively. It also displays a small Tafel slope of 44.1 mV dec−1 and remarkable stability for over 100 h at 100 and 500 mA cm−2. When used as an anode, a two-electrode electrolyzer cell with NFM30-N at 500 mA cm−2 only requires a cell voltage of 1.619 V and exhibits excellent stability, with almost no performance degradation after continuous chronopotentiometry test for each 100 h at 500 and 100 mA cm−2. This exceptional OER electrocatalytic performance is attributed to the integrated structure providing high electrical conductivity and stability, the presence of numerous active sites due to dealloying and the amorphous structure, and the promotion of the OER process by M–O, M–OH, and M–OOH species. This work offers a novel idea for fabricating integrated, industrially relevant electrocatalytic electrodes through traditional metallurgy combined with dealloying-oxidation.

Enhance the performance of OER electrocatalyst via synergistic oxygen vacancies and NiFe2O4-phosphorene heterostructure

The exfoliated black phosphorus nanosheets (EBP, phosphorene) is considered as a highly anticipated electrocatalyst for oxygen evolution reaction (OER) because of its unique electron structure. However, the poor stability and conductivity of EBP limit its application potential. In this paper, a heterostructure of EBP and nickel ferrite with oxygen vacancies (NFO-V-EBP) is designed by using a simple ultrasound and electronic regulation of EBP. NFO-V forms P-Ni bonds and P-O-M (M=Ni/Fe) bonds by interacting with the active lone pair electrons on the surface of EBP, which passivates EBP to improve its stability and provide more active sites. In situ Raman testing is used to assist in demonstrating the cooperative effect of EBP and oxygen vacancy, which reduced the potential barrier of OER reaction. NFO-V-EBP heterostructure exhibits excellent electrocatalytic performance for alkaline OER, showing overpotential of 243 mV at current density of 10 mA cm-2 and Tafel slope of 39 mV dec-1. It also has excellent long-term stability, at a density of 10 mA cm-2 with no significant increase in overpotential observed after nearly 100 hours under the chronoamperometric method.

Self-Assembled Conjugated Coordination Polymer Nanorings: Role of Morphology and Redox Sites for the Alkaline Electrocatalytic Oxygen Evolution Reaction.

Electrocatalytic water splitting provides a sustainable method for storing intermittent energies, such as solar energy and wind, in the form of hydrogen fuel. However, the oxygen evolution reaction (OER), constituting the other half-cell reaction, is often considered the bottleneck in overall water splitting due to its slow kinetics. Therefore, it is crucial to develop efficient, cost-effective, and robust OER catalysts to enhance the water-splitting process. Transition-metal-based coordination polymers (CPs) serve as promising electrocatalysts due to their diverse chemical architectures paired with redox-active metal centers. Despite their potential, the rational use of CPs has faced obstacles including a lack of insights into their catalytic mechanisms, low conductivity, and morphology issues. Consequently, achieving success in this field requires the rational design of ligands and topological networks with the desired electronic structure. This study delves into the design and synthesis of three novel conjugated coordination polymers (CCPs) by leveraging the full conjugation of terpyridine-attached flexible tetraphenylethylene units as electron-rich linkers with various redox-active metal centers [Co(II), Ni(II), and Zn(II)]. The self-assembly process is tuned for each CCP, resulting in two distinct morphologies: nanosheets and nanorings. The electrocatalytic OER performance efficiency is then correlated with factors such as the nanostructure morphology and redox-active metal centers in alkaline electrolytes. Notably, among the three morphologies studied, nanorings for each CCP exhibit a superior OER activity. Co(II)-integrated CCPs demonstrate a higher activity between the redox-active metal centers. Specifically, the Co(II) nanoring morphology displays exceptional catalytic activity for OER, with a lower overpotential of 347 mV at a current density of 10 mA cm-2 and small Tafel slopes of 115 mV dec-1. The long-term durability is demonstrated for at least 24 h at 1.57 V vs RHE during water splitting. This is presumably the first proof that links the importance of nanostructure morphologies to redox-active metal centers in improving the OER activity, and it may have implications for other transdisciplinary energy-related applications.

Self-supported low-crystallinity CoFe layered double hydroxide nanospheres on monolayer Ti3C2 electrode for oxygen evolution reaction

The electrocatalytic oxygen evolution reaction is a crucial means to support the conversion and storage of the sustainable renewable energy. Low-crystallinity can offer short-range structural ordering and high active site density. In this work, an efficient self-supported oxygen evolution reaction (OER) electrocatalyst, cobalt iron layered double hydroxide (LDH) grown on Ti3C2 modified nickel foam (NF) heterostructure anode (CoFe-LDH/Ti3C2/NF) was prepared using electrodeposition. The exceptional electrocatalytic OER performance is ensured by in situ decorating monolayer Ti3C2/NF (s-Ti3C2/NF) with low-crystallinity CoFe nanospheres. By harnessing the low crystallinity, well-chosen composition and reasonable heterostructure, the overpotential of CoFe-LDH/Ti3C2/NF decreases to 246 mV at a current density of 10 mA·cm−2 in alkaline media. After 3000 cyclic voltammograms cycles, the ignorable increase in overpotential of 14 mV suggest the excellent long circular stability. Moreover, an accelerated reaction kinetics is implied by the smaller Tafel slope (28.76 mV·dec−1) and higher double-layer specific capacitance (2.33 mF·cm−2), which surpassed the counterparts CoFe-LDH grown on NF (CoFe-LDH/NF) and s-Ti3C2/NF. This work paves a new way to fabricate the low-crystallinity materials for electrocatalysis and energy storage.

Self-supported monometallic FeS2/FeOOH-ZnO@NF with abundant oxygen vacancies as efficient and stable electrocatalysts for the OER and HER

The construction of heterogeneous interfaces and oxygen vacancy (Ov) is a very useful method to enhance the catalytic activity performance of catalysts. In this work, the high-performance a monometallic iron based bifunctional electrocatalyst FeS2/FeOOH-ZnO@NF with oxygen vacancy (Ov) and heterogeneous interface is prepared by the ZnO template induced deposition method for the first time. Due to the synergistic effect of the heterogeneous interface of FeS2/FeOOH-ZnO@NF and the oxygen vacancies of the ZnO, the FeS2/FeOOH-ZnO@NF catalysts exhibited excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity in alkaline media, with a low overpotential of 74 mV and 177 mV at 10 mA cm−2, respectively. It should be emphasized that the FeS2/FeOOH-ZnO@NF || FeS2/FeOOH-ZnO@NF electrolytic cell has an ultra-low decomposition voltage, only 1.41 V at 10 mA cm−2 and 1.49 V at 20 mA cm−2, which is much lower than that currently reported in most literatures. This work will provide a new strategy and idea for the improvement of HER and OER electrocatalytic performance of transition metal-based catalyst.

Laser-Induced Preparation of Anderson-Type Polyoxometalate-Derived Sulfide/Oxide Electrocatalysts for Electrochemical Water Oxidation.

Developing cost-effective and high-active electrocatalysts is vital to enhance the electrocatalytic performance for oxygen evolution reaction (OER). However, traditional pyrolysis methods require complicated procedures, exact temperatures, and long reaction times, leading to high costs and low yields of electrocatalysts in potential industrial applications. Herein, a rapid and economic laser-induced preparation strategy is proposed to synthesize three bimetallic sulfide/oxide composites (MMoOS, M=Fe, Co, and Ni) on a nickel foam (NF) substrate. A focused CO2 laser with high energy is applied to decompose Anderson-type polyoxometalate (POM)-based precursors, enabling the creation of abundant heteropore and defective structures in the MMoOS composites that have multi-components of MS/Mo4O11/MoS2. Remarkably, owing to the structural interactions between the active species, FeMoOS shows superior electrocatalytic performance for OER in an alkaline medium, exhibiting a low overpotential of 240 mV at 50 mA cm-2, a small Tafel slope of 79 mV dec-1, and good durability for 80 h. Physical characterizations after OER imply that partially dissolved Mo-based species and new-formed NiO/NiOOH can effectively uncover abundant active sites, fasten charge transfer, and modify defective structures. This work provides a rapid laser-induced irradiation method for the synthesis of POM-derived nanocomposites as promoted electrocatalysts.

Template-assisted strategy for synthesizing transition metal oxyhydroxide for high-efficiency oxygen evolution reaction

Oxyhydroxides have been widely recognized as the true active species for oxygen evolution reaction (OER), while most of them are created via the complicated and time-consuming electrochemical activation process. Here, we develop a facile template-mediated method for directly synthesizing highly active oxyhydroxides toward OER. The optimal FeCoOOH prepared via using Cu2O as a sacrificial template could exhibit outstanding electrocatalytic OER performance, delivering a current density of 10 mA cm−2 with the overpotential of merely 320 mV, and a corresponding Tafel slope of 77.5 mV dec−1. Detailed mechanism study outlines that the extraordinary OER performance of such FeCoOOH originated from the intrinsically high OER activity of oxyhydroxide and the high specific surface area of the particular architecture. This work demonstrates a simple and direct route for the successful fabrication of highly active oxyhydroxides, which may open a new way for the synthesis of other active species.

Bifunctional activity and theoretical study of transition metal molybdates for hydrogen and oxygen evolution reaction

Effective, sturdy and cheap electrocatalysts are extremely desirable for water electrolysis. In this work, transition metal molybdates (MMoO4, M = Fe, Co, Ni) with extraordinary oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in basic electrolyte solution was reported. β-Fe2(MoO4)3 catalyst exhibits better electrocatalytic performance and robustness for both HER and OER compared to NiMoO4 and CoMoO4. Theoretical study (DFT calculation) disclose that the Fe atoms increase the energy states near the Fermi level in β-Fe2(MoO4)3 which makes it more conductive leading to superior OER and HER activity. Compared to CoMoO4 and NiMoO4, β-Fe2(MoO4)3 have well defined multiple Mo 4d orbitals at the conduction band. These are empty states in conduction band, ready to receive the electrons. Further, the computed overpotential values for NiMoO4, CoMoO4, and β-Fe2(MoO4)3 surfaces follow the trend, β-Fe2(MoO4)3 < NiMoO4 < CoMoO4, corroborating with the experimental results.

Cr dopant regulating d-orbital electronic configuration of NiFe spinel oxide to improve oxygen evolution reaction in Zn-air battery

Significant advancements towards enhancing the catalytic activity of spinel ferrites in oxygen evolution reaction (OER) have been achieved, however, further studies are required on this regard. In this study, Cr-doped spinel ferrite (NiFe2O4) embedded in N-doped C (Cr-NiFe2O4@NC) was synthesized via a high-temperature treatment using an NiFe Prussian blue analog as a precursor and K2Cr2O7 as a Cr source. Owing to the strong octahedral site preference energy, Cr3+ ions were successfully doped into octahedral sites and tailored the electronic configuration of NiFe2O4, as confirmed by XPS. The Cr-substituted Cr-NiFe2O4@NC exhibited the overpotential of 241 mV at 10 mA cm−2, which was smaller than that of NiFe2O4@NC (266 mV) at the same current density. Meanwhile, the Tafel slope of Cr-NiFe2O4@NC (65.32 mV dec−1) was also lower than that of NiFe2O4@NC (86.96 mV dec−1). Therefore, the Cr substitution can improve the electrocatalytic OER performance of NiFe2O4@NC. In particular, an assembled rechargeable Zn-air battery using Cr-NiFe2O4@NC as the cathode catalyst afforded a high power density (61.1 mA cm−2) together with a high specific capacity (740 mA g−1). Amazingly, it could power light-emitting diodes, demonstrating its real-world application. Density functional theory calculations revealed that Cr ion doping led to electron transfer in NiFe2O4, resulting in a density of electronic states close to the Fermi level, which probably regulated the adsorption/desorption behaviors of oxygenate intermediates (*O and *OOH), thus promoting the reaction kinetics of the OER. This study provides a helpful basis for the development of spinel oxides with high electrocatalytic OER activity and durability via cation doping.

Synergistic RB5 dye degradation and oxygen evolution reaction (OER) catalysis by WO3 nano-pellets: mechanistic insights and water remediation applications

Transition metal oxides (TMO), a non-noble element based oxides, establish remarkable potential in the realm of textile wastewater remediation and water splitting due to their sustainable catalytic performance. Highly functional TMO materials, in form of nanostrcutures, are of great interest owing to their robust photo and electro-catalytic activities for instituting sustainable development for the water and energy resource management framework. In the present article, we have reported catalytically active WO3 nano-pellets (NP) synthesized using microwave-assisted for photocatalytic wastewater remediation and electrocatalytic oxygen evolution reaction (OER). Promisingly, WO3 NP abetted degradation of the reactive black 5 (RB5) dye by almost 95 % in short time interval of 60 min in exposer of sun light. Present work includes the strategies to remove and observe the progression of reaction kinetics of dye degradation in neutral and alkaline media. By varying concentration of the catalyst (ranging from 250 mg/L to 1000 mg/L, in the step of 250 mg/L), we have prolifically verified that 750 mg/L turn out optimal dosage for 100% degradation in time interval of 120 min. Besides, WO3 NP has shown highest photocatalytic behaviour at 9 pH. The WO3 NP shows the electrocatalytic OER performance in an alkaline condition (1M KOH) with an overpotential of 418 mV to generate the geometric current density of 10 mA/cm² and Tafel slope of 178 mV dec⁻¹. Owing to robust nature, WO3 NP shows the almost similar photocatalytic response for ten cycles dye degradation and demonstrates the stable electrochemical charge transport for OER at 10 mA/cm2 for 50 hours.

Bi-functional CoCr2O4 hollow-sphere for enhanced oxygen evolution reaction and photocatalyst for harmful environmental pollutants removal

The development of a high-performance, cost-effective, and durable multifunctional semiconductor is crucial for clean energy and environmental remediation applications such as oxygen evolution reaction (OER) and photocatalysts. In this research, we have developed a hollow sphere-based spinel-structured CoCr2O4 (HS.CCO) for bi-functional applications. These hollow spheres exhibit excellent electrocatalytic OER performance under an alkaline (1 M potassium hydroxide (KOH)) medium, which displays a higher electrocatalytic ability. The spinel hollow spheres demonstrate favorable overpotentials and Tafel potentials of 180 mV and 162 mV/dec, respectively towards OER activity. On the other hand, as a photocatalysis, they portrayed outstanding degradation efficiency under visible light irradiation towards Congo red (CR) dye degradation. Within the short treatment time higher CR degradation efficiency is achieved. These photo-electroactive spinel hollow spheres accelerate efficient OER and visible-light-driven photocatalysis with remarkable stability. They serve as an excellent example of a multifunctional heterogeneous catalyst. Finally, the obtained results indicate the current needs and future demands for enhancing the prospects of multifunctional semiconductor catalysts.

Carbon Nanotube Composites with Bimetallic Transition Metal Selenides as Efficient Electrocatalysts for Oxygen Evolution Reaction

Hydrogen fuel is a clean and versatile energy carrier that can be used for various applications, including transportation, power generation, and industrial processes. Electrocatalytic water splitting could be the most beneficial and facile approach for producing hydrogen. In this work, transition metal selenide composites with carbon nanotubes (CNTs) have been investigated for electrocatalytic water splitting. The synthesis process involved the facile one-step hydrothermal growth of transition metal nanoparticles over the CNTs and acted as an efficient electrode toward electrochemical water splitting. Scanning electron microscopy and XRD patterns reveal that nanoparticles were firmly anchored on the CNTs, resulting in the formation of composites. The electrochemical measurements reveal that CNT composite with nickel–cobalt selenides (NiCo-Se/CNTs@NF) display remarkable oxygen evolution reaction (OER) activity in basic media, which is an important part of hydrogen production. It demonstrates the lowest overpotential (η10mAcm−2) of 0.560 V vs. RHE, a reduced Tafel slope of 163 mV/dec, and lower charge transfer impedance for the OER process. The multi-metallic selenide composite with CNTs demonstrating unique nanostructure and synergistic effects offers a promising platform for enhancing electrocatalytic OER performance and opens up new avenues for efficient energy conversion and storage applications.

Co/Co3O4 Heterojunctions Encased in Porous N-Doped Carbon Nanocapsules for High-Performance Cathode of Rechargeable Zinc-Air Batteries.

A long-term goal of rechargeable zinc-air batteries (ZABs) has always been to design bifunctional electrocatalysts that are robust, effective, and affordable for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It has become a feasible method to construct metal/metal oxide interfaces to achieve superior electrocatalytic performance for ORR and OER by enhanced charge transfer. In this study, Co/Co3O4 heterojunctions were successfully prepared and encased in porous N-doped mesoporous carbon (Co/Co3O4@NC) via a simple condensation-carbonization-etching method. The extensive specific surface area of Co/Co3O4@NC facilitates effective interaction between the electrolyte and the catalyst, thereby enabling sufficient exposure of active sites for the ORR and the OER, consequently enhancing the rate of transport of active species. The well-designed Co/Co3O4@NC delivers superior ORR catalytic activity with a half-wave potential of 0.82 V (vs RHE) and a low overpotential of 347 mV at 10 mA cm-2 for OER in alkaline solution. The power density of Co/Co3O4@NC-based alkaline aqueous ZAB (156.5 mW cm-2) is superior to the commercial Pt/C + IrO2-based alkaline aqueous ZAB, and the cycling stability of ZAB is up to 220 h. In addition, Co/Co3O4@NC-based ZAB shows a high power density (50.1 mW cm-2). The construction of metal/metal oxide heterojunction encased in N-doped mesoporous carbon provides a novel route for the design of bifunctional electrocatalysts for high-performance ZABs.

In Situ Reconstruction of High-Entropy Heterostructure Catalysts for Stable Oxygen Evolution Electrocatalysis under Industrial Conditions.

Despite of urgent needs for highly stable and efficient electrochemical water-splitting devices, it remains extremely challenging to acquire highly stable oxygen evolution reaction (OER) electrocatalysts under harsh industrial conditions. Here, a successful in situ synthesis of FeCoNiMnCr high-entropy alloy (HEA) and high-entropy oxide (HEO) heterocatalysts via a Cr-induced spontaneous reconstruction strategy is reported, and it is demonstrated that they deliver excellent ultrastable OER electrocatalytic performance with a low overpotential of 320mV at 500mA cm-2 and a negligible activity loss after maintaining at 100mA cm-2 for 240h. Remarkably, the heterocatalyst holds outstanding long-term stability under harsh industrial condition of 6m KOH and 85°C at a current density of as high as 500mA cm-2 over 500h. Density functional theory calculations reveal that the formation of the HEA-HEO heterostructure can provide electroactive sites possessing robust valence states to guarantee long-term stable OER process, leading to the enhancement of electroactivity. The findings of such highly stable OER heterocatalysts under industrial conditions offer a new perspective for designing and constructing efficient high-entropy electrocatalysts for practical industrial water splitting.

In Situ Electrochemical Restructuring B-Doped Metal-Organic Frameworks as Efficient OER Electrocatalysts for Stable Anion Exchange Membrane Water Electrolysis.

Metal organic frameworks (MOFs) are promising as effective electrocatalysts toward oxygen evolution reaction (OER). However, the origin of OER activity for MOF-based electrocatalysts is still unclear because of their structure reconstruction during electrocatalysis process. Here, a novel MOF (B-MOF-Zn-Co) with spherical superstructure is developed by hydrothermal treatment of zeolitic imidazolate framework-Zn, Co (ZIF-Zn-Co) using boric acid. The resultant B-MOF-Zn-Co shows high OER activity with a low overpotential of 362mV at 100mA cm-2. Remarkably, B-MOF-Zn-Co displays excellent stability with only 3.6% voltage delay over 300h at 100mA cm-2 in alkaline electrolyte. Surprisingly, B-MOF-Zn-Co thoroughly transforms into B-doped CoOOH (B-CoOOH) during electrolysis process, which isserved as actual active material for high OER electrocatalytic performance. The newly-formed B-CoOOH possesses lower energy barrier of potential-determining step (PDS) for OOH* formation compared with CoOOH, benefiting for high OER activity. More importantly, B-MOF-Zn-Co based anion exchange membrane water electrolytic cell (AEMWE) demonstrates continuously durable operation with stable current density of 200mA cm-2 over 300h, illustrating its potential application in practice water electrolysis. This work offers an in situ electrochemical reconstruction strategy for the development of stable and effective OER electrocatalysts toward practice AEMWE.

Controllable morphology transformation of hierarchical-porous CoMoSi/C metal hydroxide nanosheets from sugarcane bagasse as green sources for high performance supercapacitors and oxygen evolution reaction

Dual-function electrode materials for energy production and storage require careful design of nanostructures, with several components. This study focused on developing high-performance supercapacitors (SCs) and oxygen evolution reaction (OER) electrocatalysts using metal hydroxide (MOH) nanosheets (NSs) derived from biogenic sugarcane bagasse (BSCB). The MOH NSs were transformed into hierarchically porous CoMoSi/C OH NSs catalysts via a controllable morphology transformation and carbonization process. The hierarchically porous CoMoSi/C OH NSs exhibited outstanding SCs performance, with a specific capacitance of 427 F g−1 at 0.5 Ag−1 with a 98 % capacitance retention rate for 15,000 cycles. In addition, the CoMoSi/C OH NSs catalyst attained a lower overpotential of 197 mV at 10 mA cm−2 with a Tafel value of 84 mV dec−1 towards electrocatalytic OER performance. Therefore, this study demonstrated the potential use of bio-derived electrocatalysts with controllable morphological transformations for the development of high-performance electrode materials for energy applications.

Nickel molybdate/cobalt iron carbonate hydroxide heterojunction with oxygen vacancy enables interfacial synergism to trigger oxygen evolution reaction

The development of electrocatalysts with excellent performance toward oxygen evolution reaction (OER) for the production of hydrogen is of great significance to alleviate energy crisis and environmental pollution. Herein, the heterostructure (NMO/FCHC-0.4) was fabricated by the coupling growth of NiMoO4 (NMO) and cobalt iron carbonate hydroxide (FCHC) on nickel foam as an electrocatalyst for OER. The interfacial synergy on NMO/FCHC-0.4 heterojunction can promote the interfacial electron redistribution, affect the center position of d band, optimize the adsorption of intermediate, and improve the conductivity. Beyond, oxygen defect sites are conducive to the adsorption of intermediates, and increase the number of active sites. Real-time OER kinetic simulation revealed that the interfacial synergism and molybdate could reduce the adsorption of hydroxide, promote the deprotonation step of M-OH, and facilitate the formation of M-OOH (M represents the metal active site). As a result, NMO/FCHC-0.4 displays excellent OER electrocatalytic performance with an overpotential of 250/280 mV at the current density 100/200 mA cm−2 and robust stability at 100 mA cm−2 for 100 h. This work provides deep insights into the roles of interfacial electronic modulation and oxygen vacancy to design high-efficiency electrocatalysts for OER.

Tuning electronic structure of hedgehog-like nickel cobaltite via molybdenum-doping for enhanced electrocatalytic oxygen evolution catalysis

As a typical spinel oxide, nickel cobaltite (NiCo2O4) is considered to be a promising and reliable oxygen evolution reaction (OER) catalyst due to its abundant oxidation states and the synergistic effect of multiple metal species. However, the electrocatalytic OER performance of NiCo2O4 has always been limited by the low specific surface area and poor intrinsic conductivity of spinels. Herein, the hedgehog-like molybdenum-doped NiCo2O4 (Mo-NiCo2O4) catalyst was prepared as an efficient OER electrocatalyst via a facile hydrothermal method followed with high-temperature annealing. The Mo-NiCo2O4-0.075 with Mo doping concentration of ∼ 1.95 wt% exhibits excellent OER performance with a low overpotential of 265 mV at a current density of 10 mA·cm−2and a Tafel slope of 126.63 mV·dec-1, as well as excellent cyclingstability.The results demonstrated that the hedgehog-like structure provides Mo-NiCo2O4 with the high surface area and mesopores that enhance electrolyte diffusion and optimal active site exposure. The in-situ Raman spectra and density functional theory calculations show that the Mo cations doping improve the intrinsic conductivity of the NiCo2O4 while modulating the chemisorption of intermediates. Meanwhile, the energy barriers of *OH and O* formation decrease significantly after Mo doping, effectively facilitating water dissociation and optimizing the reaction kinetics.

Self-reconstruction in self-supporting MOF-74 electrode to enhance electrocatalytic oxygen evolution

Understanding the self-reconstruction process of metal-organic frameworks (MOFs) in alkaline electrolytes is extremely important for the development of efficient electrocatalysts for the oxygen evolution reaction (OER). In this study, we synthesized MOF-74 in-situ on activated nickel-iron foam (NFF) to create a self-supporting MOF-74/NFF(40) electrode without the need for an imposed metal species. It was found that the prepared MOF-74/NFF(40) electrode possessed the best electrocatalytic OER performance, which can achieve the current density of 10, 50, 100 mA cm−2 in 1 M KOH at overpotentials of 227,295 and 357 mV, respectively. X-ray photoelectron spectroscopy (XPS) revealed that the OER process altered the local electron structure of Fe and Ni atoms, resulting in electron transfer from Fe to Ni and promoting oxygen production through bimetallic synergy. Furthermore, the electrochemical reconstruction process on the electrode surface in-situ generated metal hydroxides and hydroxyl oxides, which acted as the main active species to accelerate OER. This study presents a simple and effective approach for synthesizing high-performance and long-lasting MOF-based electrocatalysts for OER.