Chen Changwei, Kosari Mohammadreza, Jiang Zeyu, Xi Shibo, Xia Lianghui, Shao Yuying, He Chi, Zeng Hua Chun
Xi'an University of Science and Technology, Xi'an, Shannxi, 710054, P.R. China.
State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, Shannxi, 710049, P.R. China.
Small. 2025 May;21(20):e2412786. doi: 10.1002/smll.202412786. Epub 2025 Apr 7.
The controlled creation, selective exposure, and activation of more Cu─ZnO interface while simultaneously minimizing copper usage are crucial for accelerating methanol synthesis from CO hydrogenation over Cu─ZnO-AlO catalysts. Employing layered double oxides (LDO) as the support with intrinsically structured ZnAl, herein, an efficient triphasic catalyst bearing extrinsically deposited ultrafine Cu nanoparticles derived from metal-organic framework (MOF), manifesting a rich Cu─ZnO interface when compared to identically synthesized counterparts with limited and regular interfaces is presented. The resulting 2D catalyst with the maximized interface between Cu crystallites and LDO gallery (C/ZALDO) dramatically raises the rate of CO hydrogenation to methanol with a remarkable methanol space-time yield of 1612 g·kg ·h at 260 °C and 30 bar. Ex situ characterizations and in situ spectroscopy results confirm that methanol is produced from the hydrogenation of carbon monoxide (CO*) intermediate (via RWGS+CO-hydro pathway) which is stably adsorbed on the Cu─ZnO interface.
在使用铜锌铝催化剂通过一氧化碳加氢合成甲醇的过程中，控制铜-氧化锌界面的生成、选择性暴露和活化，同时尽量减少铜的用量，对于加速反应至关重要。本文采用具有本征结构锌铝的层状双氧化物（LDO）作为载体，制备了一种高效的三相催化剂，该催化剂含有从金属有机框架（MOF）衍生而来的外在沉积的超细铜纳米颗粒，与具有有限且规则界面的相同合成对应物相比，表现出丰富的铜-氧化锌界面。由此产生的二维催化剂在铜微晶和LDO层间（C/ZALDO）之间具有最大化的界面，在260°C和30巴的条件下，将一氧化碳加氢制甲醇的速率显著提高，甲醇时空产率达到1612 g·kg⁻¹·h。非原位表征和原位光谱结果证实，甲醇是由稳定吸附在铜-氧化锌界面上的一氧化碳（CO*）中间体通过逆水煤气变换+一氧化碳加氢途径加氢生成的。
