Study of Non-Noble-Metal-Based Metal–Nitrogen–Carbon Catalysts for Formic Acid Dehydrogenation
Qiaoyu Zhang, Qiufeng Mao, Yunpeng Zhou, Liangyu Zou, Daoyun Zhu, Yangqiang Huang, Hongxia Gao, Xiao Luo, Yu Mao, Zhiwu Liang
Abstract
Formic acid (FA) is a safe, renewable, and promising hydrogen carrier. A critical challenge is the effective screening of the suitable non-noble-metal-based catalysts for FA dehydrogenation to substitute expensive noble-metal-based ones. Here, a study of all possible catalysts with M–N–C structures (M = 12 metals, −N–C = nitrogen-doped graphene-like surface) for FA dehydrogenation has been conducted using density functional theory (DFT) and followed by experimental analysis. Based on the adsorption energy of critical intermediates, preliminary screening suggests Co as a possible active metal for M–N–C. Experiment and further DFT calculations suggest that atomically dispersed Co sites (Co–N1–C3, Co–N2–C2, and Co–N3–C) are preferable for FA dehydrogenation. The appropriate N contents are critical to the catalytic activity, whose amount can be tuned by choosing different sacrifice templates and the pyrolysis temperature.