Zhang Xibo, Yu Xiang, Mendes Rafael G, Matvija Peter, Melcherts Angela E M, Sun Chunning, Ye Xinwei, Weckhuysen Bert M, Monai Matteo
Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
State Key Laboratory of Physical Chemistry of Solid Surfaces & Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416899. doi: 10.1002/anie.202416899. Epub 2024 Nov 13.
ZnO/ZrO catalysts have shown better activity in the CO hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO is still poorly understood. In particular, the effect of the ZrO support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO catalysts supported on tetragonal ZrO (ZnO/ZrO-t) and monoclinic ZrO (ZnO/ZrO-m), which resulted in the formation of different ZnO species, consisting of sub-nanometer ZnO moieties and large-sized ZnO particles, respectively. ZnO/ZrO-t exhibited a higher methanol selectivity (81 vs. 39 %) and methanol yield (1.25 vs. 0.67 mmol g h) compared with ZnO/ZrO-m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO-t had a high density of ZnO-ZrO sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO-t during catalysis, while larger ZnO particles on ZnO/ZrO-m remained stable throughout the reaction. This study shows that the phase of ZrO supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.
与单一组分的催化剂相比，ZnO/ZrO催化剂在CO加氢制甲醇反应中表现出更好的活性，但ZnO与ZrO之间的相互作用仍未得到充分理解。特别是，ZrO载体相（四方相与单斜相）的影响尚未得到系统研究。在此，我们合成了负载在四方ZrO（ZnO/ZrO-t）和单斜ZrO（ZnO/ZrO-m）上的ZnO/ZrO催化剂，这导致分别形成了由亚纳米级ZnO部分和大尺寸ZnO颗粒组成的不同ZnO物种。与ZnO/ZrO-m相比，ZnO/ZrO-t表现出更高的甲醇选择性（81%对39%）和甲醇产率（1.25 mmol g⁻¹ h⁻¹对0.67 mmol g⁻¹ h⁻¹）。基于光谱和显微镜结果，性能差异归因于Zn的氧化还原状态和分散程度。ZnO/ZrO-t具有高密度的ZnO-ZrO位点，有利于活性HCOO*物种的形成，并提高了沿甲酸盐途径的甲醇产率和选择性。在催化过程中，此类ZnO簇进一步分散在ZrO-t上，而ZnO/ZrO-m上较大的ZnO颗粒在整个反应过程中保持稳定。这项研究表明，ZrO载体的相可用于控制ZnO的分散和催化剂表面化学性质，并提高催化性能。
