Modulating Electronic Structure by Etching Strategy to Construct NiSe2 /Ni0.85 Se Heterostructure for Urea-Assisted Hydrogen Evolution Reaction.

Exploring and developing novel strategies for constructing heterostructure electrocatalysts is still challenging for water electrolysis. Herein, a creative etching treatment strategy is adopted to construct NiSe2 /Ni0.85 Se heterostructure. The rich heterointerfaces between NiSe2 and Ni0.85 Se emerge strong electronic interaction, which easily induces the electron transfer from NiSe2 to Ni0.85 Se, and tunes the charge-state of NiSe2 and Ni0.85 Se. In the NiSe2 /Ni0.85 Se heterojunction nanomaterial, the higher charge-state Ni0.85 Se is capable of affording partial electrons to combine with hydrogen protons, inducing the rapid formation of H2 molecule. Accordingly, the lower charge-state NiSe2 in the NiSe2 /Ni0.85 Se heterojunction nanomaterial is more easily oxidized into high valence state Ni3+ during the oxygen evolution reaction (OER) process, which is beneficial to accelerate the mass/charge transfer and enhance the electrocatalytic activities towards OER. Theoretical calculations indicate that the heterointerfaces are conducive to modulating the electronic structure and optimizing the adsorption energy toward intermediate H* during the hydrogen evolution reaction (HER) process, leading to superior electrocatalytic activities. To expand the application of the NiSe2 /Ni0.85 Se-2h electrocatalyst, urea is served as the adjuvant to proceed with the energy-saving hydrogen production and pollutant degradation, and it is proven to be a brilliant strategy.

Modulating metal-support interaction and inducing electron-rich environment of Ni2P NPs by B atoms incorporation for enhanced hydrogen evolution reaction performance.

Modulation of the electronic interaction between the metal and support has been verified as a feasible strategy to improve the electrocatalytic performance of supported-type catalysts. Here, we have successfully synthesized an electrocatalyst of Ni2P nanoparticles (NPs) anchored on B, N co-doped graphite-like carbon nanosheets (Ni2P@B, N-GC), and elucidated the main mechanism by which B atoms doping enhances electrocatalytic hydrogen evolution reaction (HER) performance. The B atoms with electron-rich characteristic not only modulate the electronic structure on carbon skeleton, but also regulate the interfacial electronic interaction between Ni2P NPs and the carbon skeleton, which can lead to the increased available electron density of Ni sites. Such optimization is conducive to accelerating proton transfer and promoting reactive activity. As revealed, the Ni2P@B, N-GC catalyst with B atoms doping exhibits superior performance to the Ni2P@N-GC catalyst in acidic, neutral and alkaline medias. In addition, the assembled Ni(OH)2@B, N-GC||Ni2P@B, N-GC electrolyzer displays prominent overall water splitting performance in alkaline solution, which only demands 1.57 V to reach 10 mA/cm2, and in complicated natural seawater electrolyte, as low as 1.59 V. Hence, the B atoms doping strategy shows the significant enhancement for HER electrocatalysis.

Constructing abundant interfaces by decorating MoP quantum dots on CoP nanowires to induce electronic structure modulation for enhanced hydrogen evolution reaction.

Interface engineering is a method of enhancing catalytic activity while maintaining a material's surface properties. Thus, we explored the interface effect mechanism via a hierarchical structure of MoP/CoP/Cu3P/CF. Remarkably, the heterostructure MoP/CoP/Cu3P/CF demonstrates an outstanding overpotential of 64.6 mV at 10 mA cm-2 with a Tafel slope of 68.2 mV dec-1 in 1 M KOH. DFT calculations indicate that the MoP/CoP interface in the catalyst exhibited the most favorable H* adsorption characteristics (-0.08 eV) compared to the pure phases of CoP (0.55 eV) and MoP (0.22 eV). This result can be attributed to the apparent modulation of electronic structures within the interface domains. Additionally, the CoCH/Cu(OH)2/CF‖MoP/CoP/Cu3P/CF electrolyzer demonstrates excellent overall water splitting performance, achieving 10 mA cm-2 in 1 M KOH solution with a modest voltage of only 1.53 V. This electronic structure adjustment via interface effects provides a new and efficient approach to prepare high-performance hydrogen production catalysts.

Recent advances in interface engineering of Fe/Co/Ni-based heterostructure electrocatalysts for water splitting.

Among various methods of developing hydrogen energy, electrocatalytic water splitting for hydrogen production is one of the approaches to achieve the goal of zero carbon emissions. It is of great significance to develop highly active and stable catalysts to improve the efficiency of hydrogen production. In recent years, the construction of nanoscale heterostructure electrocatalysts through interface engineering can not only overcome the shortcomings of single-component materials to effectively improve their electrocatalytic efficiency and stability but also adjust the intrinsic activity or design synergistic interfaces to improve catalytic performance. Among them, some researchers proposed to replace the slow oxygen evolution reaction at the anode with the oxidation reaction of renewable resources such as biomass to improve the catalytic efficiency of the overall water splitting. The existing reviews in the field of electrocatalysis mainly focus on the relationship between the interface structure, principle, and principle of catalytic reaction, and some articles summarize the performance and improvement schemes of transition metal electrocatalysts. Among them, few studies are focusing on Fe/Co/Ni-based heterogeneous compounds, and there are fewer summaries on the oxidation reactions of organic compounds at the anode. To this end, this paper comprehensively describes the interface design and synthesis, interface classification, and application in the field of electrocatalysis of Fe/Co/Ni-based electrocatalysts. Based on the development and application of current interface engineering strategies, the experimental results of biomass electrooxidation reaction (BEOR) replacing anode oxygen evolution reaction (OER) are discussed, and it is feasible to improve the overall electrocatalytic reaction efficiency by coupling with hydrogen evolution reaction (HER). In the end, the challenges and prospects for the application of Fe/Co/Ni-based heterogeneous compounds in water splitting are briefly discussed.

Dual Atoms (Fe, F) Co-Doping Inducing Electronic Structure Modulation of NiO Hollow Flower-Spheres for Enhanced Oxygen Evolution/Sulfion Oxidation Reaction Performance.

Heteroatoms Fe, F co-doped NiO hollow spheres (Fe, F-NiO) are designed, which simultaneously integrate promoted thermodynamics by electronic structure modulation with boosted reaction kinetics by nano-architectonics. Benefiting from the electronic structure co-regulation of Ni sites by introducing Fe and F atoms in NiO , as the rate-determined step (RDS), the Gibbs free energy of OH* intermediates (ΔGOH* ) for Fe, F-NiO catalyst is significantly decreased to 1.87 eV for oxygen evolution reaction (OER) compared with pristine NiO (2.23 eV), which reduces the energy barrier and improves the reaction activity. Besides, densities of states (DOS) result verifies the bandgap of Fe, F-NiO(100) is significantly decreased compared with pristine NiO(100), which is beneficial to promote electrons transfer efficiency in electrochemical system. Profiting by the synergistic effect, the Fe, F-NiO hollow spheres only require the overpotential of 215 mV for OER at 10 mA cm-2 and extraordinary durability under alkaline condition. The assembled Fe, F-NiO||Fe-Ni2 P system only needs 1.51 V to reach 10 mA cm-2 , also exhibits outstanding electrocatalytic durability for continuous operation. More importantly, replacing the sluggish OER by advanced sulfion oxidation reaction (SOR) not only can realize the energy saving H2 production and toxic substances degradation, but also bring additional economic benefits.