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Modulating the surface composition of CuZnOx catalysts via doping Al for catalyzing CO2 hydrogenation reaction.

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Title: Modulating the surface composition of CuZnOx catalysts via doping Al for catalyzing CO2 hydrogenation reaction.
Authors: Wang, Jiajun1,2 (AUTHOR), Miao, Yuanyuan1 (AUTHOR), Wang, Peng1 (AUTHOR) p_wang@fzu.edu.cn, Tao, Xiaoxia1 (AUTHOR), Bo, Fan1 (AUTHOR), Xu, Yunzhao1 (AUTHOR), Zhao, Lingling3,4 (AUTHOR) zhaolingling@imech.ac.cn, Zhang, Caihang1 (AUTHOR), Chen, Yang1 (AUTHOR), Tan, Li1 (AUTHOR) tan@fzu.edu.cn, Tsubaki, Noritatsu5 (AUTHOR) tsubaki@eng.u-toyama.ac.jp
Source: Research on Chemical Intermediates. May2026, Vol. 52 Issue 5, p3181-3199. 19p.
Subjects: Doping agents (Chemistry), Catalyst structure, Coprecipitation (Chemistry), Catalysts, Methanol production, Catalytic activity, Catalytic hydrogenation
Abstract: For the industrially promising reaction of CO2 hydrogenation toward methanol, Cu/Zn/Al-based catalysts present a potential candidate, where the surface active structure dictates the catalytic performance, guiding ongoing research into structure–activity relationships. Herein, a series of CuZnxAly (where the mol ratio of Zn/Cu = x, mol ratio of Al/Cu = y) catalysts with varying compositions was synthesized via a coprecipitation method. Physicochemical characterization revealed that a small amount of Al (CuZn0.56Al0.04) enhanced the specific surface area, improved the dispersion of Cu and Zn species, and optimized the Cu+/Cu0 ratio, as evidenced by N2 physisorption, XRD, and XPS analyses. In contrast, excessive Al content (CuZn0.23Al0.83) led to a decline in surface area, pore volume, and surface exposure of active Cu and Zn species. Catalytic performance tests showed that CuZn0.56Al0.04 achieved the highest CO2 conversion (16.2%), methanol selectivity (56.3%), and methanol space–time yield (STY) (438 gMeOH kgcat−1 h−1), outperforming that of the commercial CuZnAl catalyst. In situ DRIFTS studies confirmed that methanol synthesis proceeded via a formate (HCOO) mediated pathway, with the optimal catalyst demonstrating superior efficiency in converting key intermediates (HCO3*, CO3*, HCOO*) to the final product. The study establishes that tailored Al content is crucial for modulating catalyst surface properties and ultimately promoting catalytic performance for methanol synthesis from CO2. An optimal Al content in co-precipitated CuZnxAly catalysts optimizes the surface active structure, enabling efficient CO2-to-methanol hydrogenation via the formate pathway. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:For the industrially promising reaction of CO2 hydrogenation toward methanol, Cu/Zn/Al-based catalysts present a potential candidate, where the surface active structure dictates the catalytic performance, guiding ongoing research into structure–activity relationships. Herein, a series of CuZnxAly (where the mol ratio of Zn/Cu = x, mol ratio of Al/Cu = y) catalysts with varying compositions was synthesized via a coprecipitation method. Physicochemical characterization revealed that a small amount of Al (CuZn0.56Al0.04) enhanced the specific surface area, improved the dispersion of Cu and Zn species, and optimized the Cu+/Cu0 ratio, as evidenced by N2 physisorption, XRD, and XPS analyses. In contrast, excessive Al content (CuZn0.23Al0.83) led to a decline in surface area, pore volume, and surface exposure of active Cu and Zn species. Catalytic performance tests showed that CuZn0.56Al0.04 achieved the highest CO2 conversion (16.2%), methanol selectivity (56.3%), and methanol space–time yield (STY) (438 gMeOH kgcat−1 h−1), outperforming that of the commercial CuZnAl catalyst. In situ DRIFTS studies confirmed that methanol synthesis proceeded via a formate (HCOO) mediated pathway, with the optimal catalyst demonstrating superior efficiency in converting key intermediates (HCO3*, CO3*, HCOO*) to the final product. The study establishes that tailored Al content is crucial for modulating catalyst surface properties and ultimately promoting catalytic performance for methanol synthesis from CO2. An optimal Al content in co-precipitated CuZnxAly catalysts optimizes the surface active structure, enabling efficient CO2-to-methanol hydrogenation via the formate pathway. [ABSTRACT FROM AUTHOR]
ISSN:09226168
DOI:10.1007/s11164-026-05971-8