Water Dissociation Kinetic‐Oriented Design of Nickel Sulfides via Tailored Dual Sites for Efficient Alkaline Hydrogen Evolution

Abstract

The reaction kinetics of alkaline hydrogen evolution reactions (HER) is a trade‐off between adsorption and desorption for intermediate species (H2O, OH, and Hads). However, due to the complicated correlation between the intermediates adsorption energy and electronic states, targeted regulating the adsorption energy at the atomic level is not comprehensive. Herein, nonmetals (B, N, O, and F) are used to modulate the adsorption energy and electronic structure of Ni3S4, and propose that H2O and OH adsorption energy are correlate directly with d‐band center (εd) of transition metal Ni, and Hads adsorption energy has a linear dependence on p‐band center (εp) of nonmetal S. Direct experimental evidence is offered that in all nonmetals doping samples, Tafel slope and exchange current density can be improved regularly with the εd and εp, and F‐Ni3S4 shows the optimum activity with tiny overpotential 29 and 92 mV for harvesting current density 10 and 100 mA cm−2, respectively. Furthermore, the micro‐kinetics analysis and density functional theory calculations verify that F‐doping can efficiently reduce the energy barrier of the Volmer step, eventually accelerating the HER kinetics. This work provides atomic‐level insight into the structure‐properties relationship, and opens an avenue for kinetic‐oriented design of alkaline HER and beyond.

Corrosive-coordinate engineering to construct 2D-3D nanostructure with trace Pt as efficient bifunctional electrocatalyst for overall water splitting

“…Water splitting has sparked tremendous interest owing to its sustainable, simple, and high-efficiency merits to generate highpurity H 2 gas and alleviate growing environmental and energy issues [1][2][3][4][5][6]. Nevertheless, the sluggish kinetics in anodic oxygen evolution reaction (OER) [7,8] and cathodic hydrogen evolution reaction (HER) limits the energy conversion efficiency [9][10][11][12][13][14][15], which mainly depends on the catalytic performances of electrocatalysts [16][17][18][19][20][21]. At present, noble metal Pt-and Ru/Ir-based nanomaterials are the benchmark electrocatalysts toward HER and OER [22][23][24][25][26]; however, the high price and scarcity hinder the practical commercialization of water splitting technology [27][28][29][30].…”

Multidimensional Nonstoichiometric Electrode Materials for Electrochemical Energy Conversion and Storage

“…For nonmetal doping, annealing treatment, [57][58][59] electrodeposition, [80,81] and solvothermal [62,82] are effective strategies. As the most extensively investigated dopant, nitrogen can be facilely doped into various materials by annealing the precursors under NH 3 atmosphere.…”

“…e) Turn over frequency (TOF) and f) Exchange current density as a function of the calculated ΔG H . Reproduced with permission [81]. Copyright 2020, Wiley-VCH GmbH.…”

An In Situ Artificial Cathode Electrolyte Interphase Strategy for Suppressing Cathode Dissolution in Aqueous Zinc Ion Batteries

“…High electrochemical performance, safety, and cost competitiveness are urgently needed for energy storage technologies to meet the increasing demand for smart portable electronics and electric vehicles. [ 1–3 ] Aqueous batteries have attracted increasing attention as an alternative to the currently widespread lithium ion batteries due to the safety and high ionic conductivity of aqueous electrolytes. [ 4,5 ] Among them, aqueous zinc ion batteries (AZIBs) with low‐cost, high‐abundance, and high theoretical capacity zinc anode is a promising candidate to meet the above requirements.…”