State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University

采用蒸氨法制备了镧（La）改性的负载型铜硅（Cu/SiO2）催化剂，并对其乙酸甲酯（MeOAc）气相加氢制乙醇（EtOH）的催化性能进行了研究。采用N2吸附-脱附（N2 adsorption-desorption）、X射线粉末衍射（XRD）、电感耦合等离子体发射光谱（ICP-OES）、氢气程序升温还原（H2-TPR）、傅里叶红外光谱（FT-IR）、高分辨透射电镜（HRTEM）、光电子能谱（XPS）和原子发射光谱仪（AES）等手段对催化剂进行了的表征，发现La物种的加入产生了较多的层状硅酸铜，增强了Cu和La物种之间的相互作用。La物种的加入在结构方面提高了催化剂的比表面积，降低了铜物种的粒径，提高了铜物种的分散度；在电子还原调控方面提高了Cu+的含量，增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO2催化剂相比，镧改性后Cu/SiO2催化剂的乙酸甲酯加氢性能得到大幅提升；其中La掺杂量0.5%的Cu/SiO2催化剂表现出最佳的催化性能，乙酸甲酯转化率达98.5%，乙醇的总收率为97.0%。

A series of Cu/SiO2 catalysts modified with lanthanum (La) (30Cu-nLa/SiO2, n=0, 0.5, 1 and 2) were synthesized using the ethanol (EtOH)-assisted ammonia-evaporation method; their catalytic performance in the gas-phase hydrogenation of methyl acetate (MeOAc) to produce ethanol (EtOH) was investigated. The results indicate that the catalytic performance of Cu/SiO2 can be greatly enhanced by La modification. In particular, the 30Cu-0.5La/SiO2 catalyst exhibits excellent performance in the MeOAc hydrogenation; under 230 °C, 2 MPa H2, an LHSV of 2 h−1 and an H2/MeOAc molar ratio of 20, the MeOAc conversion reaches 98.5%, with a total EtOH yield of 97.0%. The N2-sorption, XRD, ICP-OES, H2-TPR, FT-IR, TEM, XPS, and AES characterization results reveal that the introduced La metal has a strong interaction with Cu, which can promote the dispersion of the copper species on the SiO2 support. Moreover, the content of Cu+ is increased significantly, which can enhance the electronic interaction with MeOAc via the acyl and methoxide groups and thus promote the hydrogenation of MeOAc to EtOH.

国家自然科学基金（21972112，22172123）和福建省高校产学合作项目（2021H6002）资助

张传明, 李伟杰, 康金灿, 林丽娜, 李昌鑫, 李林才, 邹昊宇, 朱红平. 镧改性Cu/SiO2催化剂的乙酸甲酯高效加氢催化性能研究[J]. 燃料化学学报（中英文）, 2024, 52(2): 131-139.

ZHANG Chuanming, LI Weijie, KANG Jincan, LIN Lina, LI Changxin, LI Lincai, ZOU Haoyu, ZHU Hongping. Catalytic performance of La-modified Cu/SiO2 in the hydrogenation of methyl acetate[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 131-139.