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The rational construction of interfacial nanostructures of metal/semiconductor (MS) contacted electrocatalysts has a significant impact on improving their intrinsic activities. However, MS contacts are often plagued by a strong Fermi‐level pinning effect, resulting in the formation of the Schottky barrier that affects the adsorption of hydrogen/oxygen intermediates. Herein, an Ohmic contact between metallic Ni3S2 and semiconducting NiMoN is well‐designed, which effectively reduces the electron conduction barriers. The as‐obtained NiMoN/Ni3S2 has remarkable bifunctional water electrolysis performance. At 10 mA·cm−2, the overpotential of hydrogen evolution and oxygen evolution reaction is 70 and 154 mV, respectively. Impressively, the formation of hydroxide during surface reconstruction can avoid the chlorine evolution on the catalyst surface. At an industrial process temperature of 85 °C, it takes only 340 mV for the overall seawater splitting of 500 mA·cm−2. UPS and UV‐VIS diffuse spectra combined with theoretical calculation results confirm that the self‐driven directed electron transfer derived from the Ohmic contact can induce local electron enrichment at the interface region, thus promoting the formation of *O to *OOH. This study provides important insights into the coordinated modulation of built‐in electric fields and the preparation of efficient multifunctional catalysts with a high abundance of active sites. [ABSTRACT FROM AUTHOR]

CoS2/CeO2, exhibiting the 3d–4f orbital coupling effect, is developed and shows exceptional OER activity, with an overpotential of 140 mV at 10 mA cm−2. DFT calculation and Raman spectra show the existence of a d–p–f electron transport ladder that can accelerate electron transfer through the Co–O(S)–Ce bond, optimize the adsorption free energy, and enhance the catalytic activity. [ABSTRACT FROM AUTHOR]

Herein, a N-doped carbon-supported Co and NiFe LDH (Co-NC@NiFe LDH) array was developed, which demonstrated superior catalytic activities for both the OER and UOR in an alkaline medium. The intrinsic electron transfer is effectively regulated by the construction of a built-in electric field, which reduces the reaction energy barrier and consequently leads to a significant enhancement in electrocatalytic activity. [ABSTRACT FROM AUTHOR]

The development of efficient non-noble metal catalysts that can operate at high current densities for sluggish oxygen evolution is crucial for the large-scale commercialization of water electrolysis. Herein, we have developed a heterostructure oxygen evolution anode material that satisfies the requirements of ampere-level current density using a straightforward calcination-electroplating approach. Due to the natural p–n junction interface, a built-in electric field is induced in the Ni3P/NiFe LDH electrode, resulting in high conductivity and low gas transmission resistance. As a result of its heterogeneous structure, abundant active sites, and rapid interfacial electron transfer, this Ni3P/NiFe LDH exhibits outstanding catalytic performance, achieving an oxygen evolution current density of 1.4 A cm−2 with an ultra-low overpotential of 304 mV. DFT calculations indicate that the formed p–n junction effectively drives electron transfer and directly influences the charge density surrounding the active center, thereby enhancing intrinsic activity. This study highlights the potential use of non-noble metal-based heterojunction materials as efficient catalysts for the oxygen evolution in alkaline water electrolysis. [ABSTRACT FROM AUTHOR]

A V-doped amorphous/crystalline heterostructure of NiFe (oxy)hydroxide with nanoflower morphology is developed, which exhibits excellent OER and UOR catalytic activities. V doping changes the local charge density, lowers the reaction barrier, and optimizes the electron arrangement of the NiFe LDH catalyst. [ABSTRACT FROM AUTHOR]

Fe, Mo-doped Ni3S2 nanosheets that are derived from NiFe-LDH by structural transformation have been successfully developed. The obtained Fe, Mo-Ni3S2 exhibits a low overpotential of 67 mV to enable a current density of 10 mA cm−2 for the HER and the overpotential for the OER is only 240 mV. Besides, the current density of 10 mA cm−2 can be achieved with a voltage of 1.53 V in a two-electrode hydrolysis device. [ABSTRACT FROM AUTHOR]

Defect and interface engineering are recognized as effective strategies to regulate electronic structure and improve activity of metal sulfide. However, the practical application of sulfide is restricted by their low conductivity and rapid decline in activity derived from large volume fluctuation during electrocatalysis process. More importantly, the determination of exact active site of sulfide is complicated due to the inevitable electrochemical reconstruction. Herein, ZnS nanoparticles with Zn defect are anchored onto the surface of NiCo2S4 nanosheet to construct NiCo2S4/ZnS hybrids, which exhibit outstanding oxygen evolution performance with an ultralow overpotential of 140 mV. The anchoring of defective ZnS nanoparticles inhibit the volume expansion of NiCo2S4 nanosheet during the cycling process. Density‐functional theory reveals that the build‐in interfacial potential and Zn defect can facilitate the thermodynamic formation of *O to *OOH, thus improve their intrinsic activity. [ABSTRACT FROM AUTHOR]

CoS 2 /CeO 2 , exhibiting the 3d-4f orbital coupling effect, is developed and shows exceptional OER activity, with an overpotential of 140 mV at 10 mA cm -2 . DFT calculation and Raman spectra show the existence of a d-p-f electron transport ladder that can accelerate electron transfer through the Co-O(S)-Ce bond, optimize the adsorption free energy, and enhance the catalytic activity.

The slow kinetics of the bifunctional (OER/ORR) oxygen electrocatalyst is the bottleneck problem restricting the performance of zinc-air batteries (ZABs). The design and synthesis of an efficient and stable electrocatalyst at the air cathode to improve the performance of ZABs is of great significance for the development of sustainable energy conversion devices. Herein, we have developed a sulfur vacancy-rich Mott-Schottky catalyst (Co@Co 9 S 8 -NCNT), which shows superior ORR/OER bifunctional electrochemical activity and stability. Specifically, the OER overpotential is only 210 mV at 10 mA cm -2 , and the half-wave potential ( E 1/2 ) of ORR is up to 0.88 V. Furthermore, a ZAB has been assembled using the Co@Co 9 S 8 -NCNT, which delivers a high power density (196.7 mW cm -2 ) and an open-circuit voltage (1.501 V), showing excellent battery performance. Density functional theory calculations demonstrate that the Co@Co 9 S 8 Mott-Schottky heterojunction and S vacancy defects are beneficial to elevate the d-band central energy level to the Fermi level, significantly enhancing the adsorption/desorption capacity of oxygen-containing intermediates, thereby effectively improving the OER activity. Moreover, the N-doped carbon nanotubes can promote the continuous electron transfer between the metal and semiconductor interface. This work proposes a valid method for the construction and structural regulation of Mott-Schottky catalysts and offers new insights into the development of catalytic materials for energy conversion equipment.

Fe, Mo-doped Ni 3 S 2 nanosheets that are derived from NiFe-LDH by structural transformation have been successfully developed. The obtained Fe, Mo-Ni 3 S 2 exhibits a low overpotential of 67 mV to enable a current density of 10 mA cm -2 for the HER and the overpotential for the OER is only 240 mV. Besides, the current density of 10 mA cm -2 can be achieved with a voltage of 1.53 V in a two-electrode hydrolysis device.

Defect and interface engineering are recognized as effective strategies to regulate electronic structure and improve activity of metal sulfide. However, the practical application of sulfide is restricted by their low conductivity and rapid decline in activity derived from large volume fluctuation during electrocatalysis process. More importantly, the determination of exact active site of sulfide is complicated due to the inevitable electrochemical reconstruction. Herein, ZnS nanoparticles with Zn defect are anchored onto the surface of NiCo 2 S 4 nanosheet to construct NiCo 2 S 4 /ZnS hybrids, which exhibit outstanding oxygen evolution performance with an ultralow overpotential of 140 mV. The anchoring of defective ZnS nanoparticles inhibit the volume expansion of NiCo 2 S 4 nanosheet during the cycling process. Density-functional theory reveals that the build-in interfacial potential and Zn defect can facilitate the thermodynamic formation of *O to *OOH, thus improve their intrinsic activity., (© 2021 Wiley-VCH GmbH.)