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.

Electronic modulation and reaction-pathway optimization on three-dimensional seaweed-like NiSe@NiMn LDH heterostructure to trigger effective oxygen evolution reaction.

The development of low-cost and high-efficiency electrocatalysts for the oxygen evolution reaction (OER) is essential to produce high-purity hydrogen in large scale. Herein, a three-dimensional (3D) seaweed-like hierarchical structure was fabricated using two-dimensional (2D) NiMn LDH nanosheets wrapped on one-dimensional (1D) NiSe nanowires with nickel foam (NF) as a substrate (NiSe@NiMn LDH/NF) via hydrothermal and electrodeposition processes. Owing to the strong interfacial synergy, 3D seaweed-like hierarchical structure, higher conductivity, and strong structural stability, the NiSe@NiMn LDH/NF exhibited superior OER performance with an overpotential of 287 mV at 100 mA cm-2, and stably operated for 160 h at large current. Moreover, the overall water splitting system with NiSe@NiMn LDH/NF as the anode and Pt/C/NF as the cathode exhibited a low cell voltage of 1.59/1.64 V to reach 50/100 mA cm-2, and excellent stability for 110 h at 300 mA cm-2. The density function theory (DFT) calculations unveiled that NiSe@NiMn LDH enabled the interfacial synergy, reallocating the electron density at the interface, and further weakening the energy barrier of OH* by strengthening chemical bonds with OH* intermediates to improve the intrinsic OER activity.

Coupling effect and electronic modulation for synergistically enhanced overall alkaline water splitting on bifunctional Fe-doped CoBi/CoP nanoneedle arrays.

Designing bifunctional electrocatalysts with high efficiency and low cost for water splitting is urgently required for the production of green hydrogen. Herein, a bifunctional iron-doped cobalt borate/cobalt phosphide hybrid supported on nickel foam (Fe-CoBi/CoP/NF) was fabricated via hydrothermal and phosphating process. Benefit from the unique nanoneedle architecture for faster mass transfer, the existence of borate on CoBi for accelerating proton transfer, the moderate adsorption of H* species on CoP, Fe doping and the synergistic effect between CoBi and CoP, Fe-CoBi/CoP/NF hybrid exhibits a low overpotential of 137 mV and 260 mV at 100 mA cm-2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Moreover, Fe-CoBi/CoP/NF||Fe-CoBi/CoP/NF also presents a low cell potential of 1.65 V@100 mA cm-2 for overall alkaline water splitting and excellent durability (128 h) without decay. This work provides a new insight into the design of bifunctional electrocatalysts simultaneously through the morphological engineering and heteroatomic doping.

La and S Co-Doping Induced the Synergism of Multiphase Nickel-Iron Nanosheets with Rich Oxygen Vacancies to Trigger Large-Current-Density Oxygen Evolution and Urea Oxidation Reactions.

The development of cost-effective electrocatalysts for oxygen evolution reaction (OER) and urea oxidation reaction (UOR) is of great significance for hydrogen production. Herein, La and S co-doped multiphase electrocatalyst (LSFN-63) is fabricated by metal-corrosion process. FeOOH can reduce the formation energy of NiOOH, and enhance the stability of NiOOH as active sites for OER/UOR. The rich oxygen vacancies can increase the number of active sites, optimize the adsorption of intermediates, and improve electrical conductivity. Beyond, La and S co-doping can also regulate the electronic structure of FeOOH. As a result, LSFN-63 presents a low overpotential of 210/450 mV at 100/1000 mA cm-2 , small Tafel slope (32 mV dec-1 ), and outstanding stability under 1000 mA cm-2 @60 h, and can also display excellent OER activity with 180 mV at 250 mA cm-2 and long-term catalytic durability at 250 mA cm-2 @135 h in 30 wt% KOH under 60 °C. Moreover, LSFN-63 demonstrates remarkable UOR performance in 1 m KOH + 0.5 m urea, which just requires an ultra-small overpotential of 140 mV at 100 mA cm-2 , and maintain long-term durability over 120 h. This work opens up a promising avenue for the development of high-efficiency electrocatalysts by a facile metal-corrosion strategy.

Self-sacrificial reconstruction of MoO42- intercalated NiFe LDH/Co2P heterostructures enabling interfacial synergies and oxygen vacancies for triggering oxygen evolution reaction.

Exploring high-efficiency electrocatalysts for oxygen evolution reaction (OER) is one of the most important concerns to produce hydrogen in water electrolysis. Herein, the FNM/Co2P-0.4 heterostructure was designed as an electrocatalyst for the OER process by the combination of MoO42- intercalating NiFe LDH and Co2P on nickel foam (NF). The surface reconstruction and MoO42- leaching can induce the conversion of Co2P and NiFe LDH on FNM/Co2P-0.4 to generate Co/NiOOH with more oxygen vacancies. Beyond, CoOOH and NiOOH can also synergize to reduce the energy barrier of OER, optimize conductivity, and improve stability. The surface reconstruction and the formation of OOH⁎ were further unveiled by in-situ UV-vis absorption spectra and Fourier-transformed alternative current voltammetry (FTACV). The integration of interfacial synergies and oxygen vacancies can facilitate the adsorption/desorption of intermediates, regulate the d-band center, and expose more active sites. And as a result, FNM/Co2P-0.4 shows a significant low overpotential (240 mV) at 50 mA cm-2, a small Tafel (74 mV dec-1), low activation energy (Ea) and remarkable durability. This work provides a new pathway to improve the OER performance by using interfacial synergies and rich oxygen vacancies derived from the self-sacrificial reconstruction of heterostructured electrocatalysts.

Doping Mo into NiFe LDH/NiSe Heterostructure to Enhance Oxygen Evolution Activity by Synergistically Facilitating Electronic Modulation and Surface Reconstruction.

It is of great significance to design highly efficient electrocatalysts with abundant earth elements instead of precious metals for water splitting. Herein, Mo-doped NiFe-layered double hydroxides/NiSe heterostructure (Mo-NiFe LDH/NiSe) was fabricated by coupling Mo-doped NiFe LDH and NiSe on nickel foam (NF). The heterostructure electrocatalyst showed ultra-low overpotential (250 mV) and remarkable durability for oxygen evolution reaction (OER) at 150 mA cm-2 . Both theoretical and experimental results confirmed that Mo doping and interfacial synergism induced the interfacial charge redistribution and the lifted d-band center to weaken the energy barrier (EB) of the formation of OOH* . Mo doping also facilitated the surface reconstruction of NiFe LDH into Ni(Fe)OOH as the active sites under electro-oxidation process. This work provides a facile strategy for electronic modulation and surface reconstruction of OER electrocatalyst by transition metal doping and heterostructure generation.

Synergistic coupling of heterostructured porous CoP nanosheets with P doped NiO for highly efficient overall alkaline water splitting.

Exploring non-noble metal materials as bifunctional catalysts for water electrolysis is of great significance for the development and utilization of hydrogen energy. Herein, a flower branch-leaf shaped phosphide/oxide heterogeneous electrocatalyst located on Ni foam (CoP/P-NiO/NF) was developed through hydrothermal and phosphorization strategy. Benefiting from the strong ability to dissociate H2O molecules on P-NiO and the suitable adsorption of intermediate H species on CoP, the optimal CoP/P-NiO/NF exhibited outstanding performance with low overpotentials of 52 mV at current density of 10 mA cm-2, smaller Tafel slopes of 73.6 mV dec-1 for hydrogen evolution reaction (HER). Meanwhile, CoP/P-NiO/NF indicated 265 mV at 100 mA cm-2 with Tafel slope of 101.8 mV dec-1 for oxygen evolution reaction (OER) due to the optimal redistribution of electrons among Ni2+, Co2+ and Co3+ for favorable adsorption/desorption of oxygen-intermediates. Both HER and OER shown robust stability during 32 h without decline. The corresponding two-electrode system for overall alkaline water splitting required a low voltage of 1.6 V at 100 mA cm-2 with long stability (20 h) which is far lower than that on RuO2-Pt/C and many other reported non-noble metal electrocatalysts. This work demonstrates that the synergistic effect and morphology engineering play vital roles in the enhanced electrocatalytic performance.

Hierarchical sheet-on-sheet heterojunction array of a ß-Ni(OH)2/Fe(OH)3 self-supporting anode for effective overall alkaline water splitting.

Rationally designing high-performance non-noble metal electrocatalysts is of essence to improve energy conversion efficiency in water splitting. Herein, a unique 3D hierarchical sheet-on-sheet heterojunction between Fe(OH)3 and ß-Ni(OH)2 on pretreated Ni foam (NiFe-HD/pre-NF) was fabricated by a two-step strategy involving the interfacial hydrolysis-deposition of Fe2+ and electrodeposition of Ni2+. The presence of the Ni-O-Fe bridge at the Fe(OH)3/ß-Ni(OH)2 heterointerface can induce interfacial electronic redistribution to form Ni3+ in NiFe-HD/pre-NF, and further strengthen the adsorption of OH- and weaken the O-H bond to change the rate-determining step (RDS) for accelerating OER kinetics. Benefiting from the sheet-on-sheet architecture and dual-phase synergism on NiFe-HD/pre-NF, the optimal NiFe-HD/pre-NF exhibits excellent OER performance with a lower overpotential of 256 mV at 100 mA cm-2, a small Tafel slope of 81 mV dec-1, high intrinsic activity and robust stability. Alkaline water-splitting using NiFe-HD/pre-NF as the anode requires ultralow cell voltages of 1.62 V and 1.83 V at current densities of 100 mA cm-2 and 400 mA cm-2, respectively, which are comparable with commercial alkaline water electrolysis, and operates steadily at a current density of 100 mA cm-2 for 85 h without decay. This work proposes a facile strategy for constructing heterojunctions and modulating electronic interaction to develop electrocatalysts with new architectures.

Electronic modulation and proton transfer by iron and borate co-doping for synergistically triggering the oxygen evolution reaction on a hollow NiO bipyramidal prism.

Designing an Earth-abundant and inexpensive electrocatalyst to drive the oxygen evolution reaction (OER) for high-purity hydrogen production is of great importance. Herein, the cation (iron) and anion (borate) co-doping strategy was proposed to effectively trigger the OER performance on a low-cost NiO material. The optimal hollow Fe/Bi-NiO bipyramidal prism shows superior OER performance, and displays a low overpotential (261 mV) at 10 mA cm-2, accompanied by a low Tafel slope (46 mV dec-1), excellent intrinsic activity and robust stability. The overall alkaline water splitting using Fe/Bi-NiO/NF as an anode affords low cell voltages of 1.50 and 1.63 V at 10 and 100 mA cm-2, and operates steadily at a high current density of 100 mA cm-2 for 55 h without decay. The excellent electrocatalytic activity could be ascribed to the hollow structure to shorten the mass transfer pathway, the electronic modulation by Fe doping, the increased accessible electroactive sites created by oxygen vacancies through borate doping, and the formation of BO33--OH- to accelerate the deprotonation of OHads.