In Situ Encapsulated CuCo@M-SiO2 for Higher Alcohol Synthesis from Biomass-Derived Syngas

被引:44
作者
Chen, Gaofeng [1 ]
Feng, Yunchao [1 ]
Wang, Zhiwei [2 ]
Yan, Guihua [1 ]
Si, Zhihao [1 ]
Sun, Yong [1 ,3 ]
Tang, Xing [1 ,3 ]
Yang, Shuhua [4 ]
Lei, Tingzhou [5 ]
Zeng, Xianhai [1 ,3 ]
Lin, Lu [1 ,3 ]
机构
[1] Xiamen Univ, Coll Energy, Xiamen 361102, Peoples R China
[2] Henan Univ Technol, Sch Environm Engn, Zhengzhou 450001, Peoples R China
[3] Fujian Engn & Res Ctr Clean & High Valued Technol, Xiamen Key Lab Clean & High Valued Utilizat Bioma, Xiamen 361102, Peoples R China
[4] Henan Acad Sci, Zhengzhou 450008, Peoples R China
[5] Changzhou Univ, Inst Urban & Rural Min, Changzhou 213164, Peoples R China
关键词
heterogeneous catalysis; syngas conversion; CO hydrogenation; higher alcohols; CuCo catalyst; DIFFUSE-REFLECTANCE FTIR; CO HYDROGENATION; TERMINAL ALCOHOLS; CATALYSTS; CONVERSION; ADSORPTION; METAL; REDUCTION; INTERFACE; METHANOL;
D O I
10.1021/acssuschemeng.1c00217
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Higher alcohol synthesis (HAS) from biomass-derived syngas (CO/H-2) is of considerable interest but has a challenge to achieve a satisfying yield, as it is a competitive reaction between C-C coupling and CO insertion. Herein, we employed a solvent (dihydric alcohol) coordination-assisted impregnation strategy to synthesize a series of catalysts with Cu and Co encapsulated in ordered mesoporous SiO2 (denoted as CuCo@M-SiO2). This synthesis strategy could effectively anchor Cu and Co cations at a close distance owing to the solvent coordination effect. Additionally, the carbon derived from the thermal decomposition (inert atmosphere) of the solvent ligand portrayed a critical role in in situ reduction of Cu and Co species and synchronous confinement. It also helped structural dispersant ("spacer") and inhibited the aggregation of Cu nanoparticles (NPs). The as-prepared CuCo@M-SiO2 catalyst contained multiple types of synergistic active sites (Cu-0, Co-0, and Con+) that collaborated with each other to enhance the higher alcohol yield. It is confirmed that the CO conversion and higher alcohol selectivity were closely related to solvent-assisted ligands. Among the selected solvent ligands (ethylene glycol, 1,2-propanediol, and 1,4-butanediol), the CuCo@M-SiO2 catalyst derived from 1,2-propanediol-assisted impregnation exhibited a remarkably catalytic performance because of the appropriate confinement effect with smaller CuCo NPs. Notably, the CO conversion was as high as 82.2% with space-time yield toward 16.1 mmol gcat(-1) h(-1) of ethanol. A narrow alcohol distribution of C-1-C-3-mixed alcohols was over 97.2%. These synthetic strategies may provide new avenues for designing effective and stable catalysts for HAS.
引用
收藏
页码:5910 / 5923
页数:14
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