Sun Zhao, Shi Weizhi, Smith Louise R, Dummer Nicholas F, Qi Haifeng, Sun Zhiqiang, Hutchings Graham J
Hunan Engineering Research Center of Clean and Low-Carbon Energy Technology, School of Energy Science and Engineering, Central South University, Changsha, 410083, China.
Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF24 4HQ, United Kingdom.
Nat Commun. 2025 Apr 26;16(1):3935. doi: 10.1038/s41467-025-59127-0.
Single atom and nanocluster catalysts are extensively investigated in heterogeneous catalysis due to their high catalytic activity and atomic utilization, while their coexisting properties and potentially synergistic effect are yet to be clarified. Herein, we construct three systems of atomic-scale catalysts (xNi/MoTiAlC, x = 0.5, 1, and 1.5) for bio-ethanol reforming, which correspond to single atoms, single atoms mixed with nanoclusters, and nanoclusters. The respective hydrogen utilization efficiency of mixed-form catalyst increases by 43.7% and 29.3% compared to single atom and nanocluster catalysts. Results demonstrate that the adjacent Ni single atom facilitates electron transfer from MoTiAlC to Ni-Mo interface and raises the d-band center, thus enhancing bio-ethanol adsorption and activation; while the existence of Ni nanoclusters contributes to lowering the energy barriers of CHCHO* dehydrogenation. The catalytically active sites are Ni-Mo alloyed single atoms with adjacent Ni nanoclusters. This work provides new implications for highly activated catalytic site construction and advanced catalyst design.
单原子和纳米团簇催化剂因其高催化活性和原子利用率而在多相催化中受到广泛研究，但其共存性质和潜在的协同效应尚待阐明。在此，我们构建了三种用于生物乙醇重整的原子尺度催化剂体系（xNi/MoTiAlC，x = 0.5、1和1.5），分别对应单原子、单原子与纳米团簇混合以及纳米团簇。与单原子催化剂和纳米团簇催化剂相比，混合形式催化剂的氢利用效率分别提高了43.7%和29.3%。结果表明，相邻的镍单原子促进了电子从MoTiAlC转移到Ni-Mo界面并提高了d带中心，从而增强了生物乙醇的吸附和活化；而镍纳米团簇的存在有助于降低CHCHO*脱氢的能垒。催化活性位点是具有相邻镍纳米团簇的Ni-Mo合金化单原子。这项工作为高活性催化位点的构建和先进催化剂的设计提供了新的启示。
