深圳大学何传新研究组在研究中取得进展。他们报道了具有高活性Ni^δ+-P^δ−对的亚纳米磷化镍异质团簇用于硝酸盐还原为氨。该研究于2025年3月26日发表于国际一流学术期刊《美国化学会杂志》上。

本文报道了具有强耦合镍磷双活性位点的亚纳米异色仪作为电催化剂来促进中性NO₃^-RR。实验和理论结果表明，Ni-P异色仪的亚纳米特性促进了电子从Ni向P的转移，生成Ni^δ+-P^δ-活性对，其中Ni^δ+物种对NO₃^-RR和P^δ-调节界面水氢键网络，促进NO₃^-RR过程中水的解离，加速质子转移。结果表明，在中性NO₃^-RR条件下，Ni-P异源电极在-0.8V下的NH₃产率为0.61 mmol h^-1 cm^-2，是Ni-P纳米粒子和Ni异源电极的2.8倍和3.3倍，生成的NH₃以NH₄⁺形式存在于电解质中。本研究通过设计具有强偶联活性位点的亚纳米异色计，为促进多中间体电催化反应提供了一种有效的方法。

据介绍，中性硝酸还原反应（NO₃^-RR）对氨（NH₃）的高效电催化剂的开发对于解决由NO₃^-引起的环境问题至关重要，但由于NO₃^-RR在中性介质中的反应动力学缓慢，因此仍然具有相当大的挑战性。

附：英文原文

Title: Subnanometric Nickel Phosphide Heteroclusters with Highly Active Niδ+–Pδ Pairs for Nitrate Reduction toward Ammonia

Author: Qi Hu, Chunyan Shang, Xinbao Chen, Shuai Qi, Qihua Huo, Hengpan Yang, Chuanxin He

Issue&Volume: March 26, 2025

Abstract: The development of efficient electrocatalysts for the neutral nitrate reduction reaction (NO3–RR) toward ammonia (NH3) is essential to address the environmental issues caused by NO3– but remains considerably challenging owing to the sluggish reaction kinetics of NO3–RR in neutral media. Herein, we report subnanometric heteroclusters with strongly coupled nickel–phosphorus (Ni–P) dual-active sites as electrocatalysts to boost the neutral NO3–RR. Experimental and theoretical results reveal that the subnanometric feature of Ni–P heteroclusters promotes the electron transfer from Ni to P, generating Niδ+–Pδ active pairs, in which Niδ+ species are highly active for the NO3–RR and Pδ tunes the interfacial water hydrogen bonding network to promote the water dissociation step and accelerate proton transfer during the NO3–RR. Consequently, in the neutral NO3–RR, Ni–P heteroclusters exhibit a large NH3 yield rate of 0.61 mmol h–1 cm–2 at 0.8 V versus reversible hydrogen electrode, which is 2.8- and 3.3-fold larger than those on Ni–P nanoparticles and Ni clusters, respectively, and the generated NH3 exists as NH4+ in electrolytes. This study offers an efficient approach to boosting electrocatalytic reactions with multiple intermediates by designing subnanometric heteroclusters with strongly coupled active sites.

DOI: 10.1021/jacs.5c01455

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c01455