Designing Efficient Non-Precious Metal Electrocatalysts for High-Performance Hydrogen Production: A Comprehensive Evaluation Strategy.

Developing abundant Earth-element and high-efficient electrocatalysts for hydrogen production is crucial in effectively reducing the cost of green hydrogen production. Herein, a strategy by comprehensively considering the computational chemical indicators for H* adsorption/desorption and dehydrogenation kinetics to evaluate the hydrogen evolution performance of electrocatalysts is proposed. Guided by the proposed strategy, a series of catalysts are constructed through a dual transition metal doping strategy. Density Functional Theory (DFT) calculations and experimental chemistry demonstrate that cobalt-vanadium co-doped Ni3N is an exceptionally ideal catalyst for hydrogen production from electrolyzed alkaline water. Specifically, Co,V-Ni3N requires only 10 and 41 mV in alkaline electrolytes and alkaline seawater, respectively, to achieve a hydrogen evolution current density of 10 mA cm-2. Moreover, it can operate steadily at a large industrial current density of 500 mA cm-2 for extended periods. Importantly, this evaluation strategy is extended to single-metal-doped Ni3N and found that it still exhibits significant universality. This study not only presents an efficient non-precious metal-based electrocatalyst for water/seawater electrolysis but also provides a significant strategy for the design of high-performance catalysts of electrolyzed water.

Nitrogen-Doped MoS2/Ti3C2TX Heterostructures as Ultra-Efficient Alkaline HER Electrocatalysts.

Molybdenum disulfide (MoS2) is intrinsically inert for the hydrogen evolution reaction (HER) in alkaline media due to its electronic structures. Herein, we tune the electronic structures of MoS2 by a combined strategy of post-N doping coupled with the synergistic effect of Ti3C2TX. The as-prepared N-doped MoS2/Ti3C2TX heterostructures show remarkable alkaline HER activity with an overpotential of 225 mV at 140 mA cm-2, which ranks the N-doped MoS2/Ti3C2TX heterostructures among the best MoS2/MXene-based electrocatalysts reported for alkaline HER. The first-principles calculations indicate that the N doping can enhance the activation of nearby S sites of MoS2/Ti3C2TX and thus promote the HER process. This strategy provides a promising way to develop high-efficiency MoS2/MXene heterostructure catalysts for alkaline HER.

Tuning the Electronic Structure of the CoP/Ni2P Nanostructure by Nitrogen Doping for an Efficient Hydrogen Evolution Reaction in Alkaline Media.

As one of the most sustainable, efficient, and cleanest ways for hydrogen production, electrochemical water splitting relies heavily on cost-efficient and stable electrocatalysts. Herein, a self-supported and nitrogen-doped hybrid CoP/Ni2P was synthesized through a simple two-step hydrothermal process followed by low-temperature phosphorization and nitridation (N-CoP/Ni2P@NF). Both experimental and density functional theory calculation results suggest that nitrogen doping can tune the electrical structure of the CoP/Ni2P heterostructure and thus optimize the free energy of adsorbed H on the surface of N-CoP/Ni2P@NF and accelerate the electronic transport activity. The prepared N-CoP/Ni2P@NF exhibits excellent electrocatalytic hydrogen evolution reaction (HER) performance, which merely requires an overpotential of -46 mV at -10 mA cm-2 and shows a negligible decay after a long durability test for 72 h in alkaline (1.0 M KOH) media. Consequently, this work supplies a novel strategy with great potential for designing transition metal phosphate-based catalysts with high HER performance.

Collaborative Interface Optimization Strategy Guided Ultrafine RuCo and MXene Heterostructure Electrocatalysts for Efficient Overall Water Splitting.

Developing highly active and robust electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) is crucial for the large-scale utilization of green hydrogen. In this study, a collaborative interface optimization guided strategy was employed to prepare a metal-organic framework (MOF) derived heterostructure electrocatalyst (MXene@RuCo NPs). The obtained electrocatalyst requires overpotentials of only 20 mV for the HER and 253 mV for the OER to deliver a current density of 10 mA/cm2 in alkaline media, respectively, and it also exhibits great performance at high current density. Experiments and theoretical calculations reveal that the doped Ru introduces second active sites and decreases the diameter of nanoparticles, which greatly enhances the number of active sites. More importantly, the MXene/RuCo NPs heterogeneous interfaces in the catalysts exhibit great synergistic effects, decreasing the work function of the catalyst and improving the charge transfer rate, thus reducing the energy barrier of the catalytic reaction. This work represents a promising strategy for the development of MOF-derived highly active catalysts to achieve efficient energy conversion in industrial applications.

Co-Doped Ni3N Nanosheets with Electron Redistribution as Bifunctional Electrocatalysts for Efficient Water Splitting.

Preparation of high-activity and earth-abundant bifunctional catalysts for efficient electrochemical water splitting are crucial and challenging. Herein, Co-doped Ni3N nanosheets loaded on nickel foam (Co-Ni3N) were synthesized. The as-prepared Co-Ni3N exhibits excellent catalytic activity toward both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline media. Density functional theory (DFT) calculation reveals that Co-Ni3N with redistribution of electrons not only can facilitate the HER kinetics but also can regulate intermediates adsorption energies for OER. Specifically, the Co-Ni3N exhibits high efficiency and stable catalytic activity, with an overpotential of only 30 and 270 mV at a current density of 10 mA cm-2 for the HER and OER in 1 M KOH, respectively. This work provides strong evidence to the merit of Co doping to improve the innate electrochemical performance in bifunctional catalysts, which might have a common impact in many similar metal-metal nitride electrocatalysts.

Induction of Co2P Growth on a MXene (Ti3C2Tx)-Modified Self-Supporting Electrode for Efficient Overall Water Splitting.

It still is a challenge to create a superior and easily coupled bifunctional electrocatalyst for water splitting impelled by a low voltage. In this work, the controlled growth of Co2P NAs on the surface of a MXene (Ti3C2Tx)-modified self-supporting electrode is demonstrated as a competent and reliable bifunctional electrocatalyst for efficient water splitting. The heterointerface in Co2P@Ti3C2Tx with an optimized adsorption free energy of H*, H2O, and better conductivity can give enhanced HER (hydrogen evolution reaction) activity, with a low overpotential (42 mV) at 10 mA cm-2. Additionally, the OER (oxygen evolution reaction) activity has also been similarly strengthened by the synergy of Co2P and MXene with an overpotential of 267 mV to arrive at 10 mA cm-2. Furthermore, the excellent bifunctional electrode (Co2P@Ti3C2Tx∥Co2P@Ti3C2Tx) exhibits efficient engineering water-splitting performance (1.46 V@10 mA cm-2) in alkaline solution. This simple design can propose a promising approach to exploit precious-metal-free catalysts for energy conversion.