Supporting Information Synthesis of Robust MOF-derived Cu/SiO 2 Catalyst with Low Copper Loading via Sol-gel Method for the Dimethyl Oxalate Hydrogenation Reaction Run-Ping Ye,,, # Ling Lin, # Chong-Chong Chen,, Jin-Xia Yang, Fei Li,, Xin Zhang, De-Jing Li,, Ye-Yan Qin, Zhangfeng Zhou, and Yuan-Gen Yao *, Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China University of Chinese Academy of Sciences, Beijing 100049, P.R. China Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071, USA College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116, P.R. China # These authors contributed equally to this work and should be considered co-first authors *Corresponding Author E-mail: yyg@fjirsm.ac.cn; Tel: +86-591-63173138 1 / 13
Figure S1. N 2 adsorption-desorption isotherm (A) and pore size distribution (B) of the HKUST-1, pure SiO 2, Cu/SiO 2 -CN and Cu/SiO 2 -MOF samples. 2 / 13
Figure S2. Photos of Cu/SiO 2 -CN (A) and Cu/SiO 2 -MOF samples. 3 / 13
Figure S3. TGA curves of HKUST-1, Cu/SiO 2 -CN and Cu/SiO 2 -MOF samples under N 2 atmosphere. 4 / 13
Figure S4. SEM images of HKUST-1 (A, B), Cu/SiO2-MOF-Dried (C, D) and Cu/SiO2-CN-Dried (E, F) 5 / 13
Figure S5. TEM images and EDX mapping images of Cu/SiO 2 -MOF-Dried. 6 / 13
Figure S6. TEM images and EDX mapping images of Cu/SiO 2 -CN-Dried. 7 / 13
Figure S7. SEM images of Cu/SiO2-MOF-Calcined (A) and Cu/SiO2-CN-Calcined (B). STEM images of Cu/SiO2-MOF-Calcined (C) and Cu/SiO2-CN-Calcined (D). 8 / 13
Figure S8. NH 3 -TPD profile of pure HKUST-1. 9 / 13
Figure S9. PXRD patterns of fresh reduced Cu/SiO 2 -MOF and after stability test samples (A). TEM image with the size distribution of the used sample (B, C). 10 / 13
Table S1. Comparison of Cu/SiO 2 -MOF catalyst in DMO hydrogenation performance with different Cu-based catalysts. Catalysts ω(cu) / wt% Conv. DMO / % Selec. EG / % P /MPa T / C H 2 /DMO /mol mol -1 WLHSV TOF Lifetime / h -1 / h -1 / h Ref. Cu/SiO 2 25.0 95 90 3.0 200 80 1.2-10 Cu/SiO 2 26.2 95 90 3.0 190 80 0.75-30 Cu/SiO 2 15.8 99 >95 3.0 200 80 1.5 6.4 80 Cu/SiO 2 16.19 95 53 2.0 190 50 1.0 5.7 75 Cu/SiO 2 17.14 95 60 2.0 210 50 0.72 4.8 80 Cu/SiO 2 8.7 95 50 3.0 190 80 0.6 10.1 100 Cu/SiO 2 14.9 100 >95 3.0 200 150 0.3-140 Cu/SiO 2 9.6 95 65 3.0 200 100 0.3-23 Cu/SiO 2-650 39.8 11.8 0.9 3.0 190 150 0.3 3.3 - Cu/HMS 10.0 85 50 3.0 220 150 1.2 1.2 20 1 2 3 4 5 6 7 8 9 10 Cu/SiO 2 -MOF 7.83 99 >95 2.0 210 50 0.82 19.3 220 This work 1B-Cu-SiO 2 27.0 99 93 3.0 190 80 0.75-300 Cu/SiO 2 -TiO 2 9.7 100 >97 3.0 200 100 0.3-70 Cu-Co/HMS 10.0 100 100 3.0 220 150 1.2 5.5 150 1.0La-Cu/SiO 2 -u 15.1 99 >90 3.0 200 80 1.5 17.6 200 Cu 1 -Ag 0.05 /SiO 2 7.3 99 >95 3.0 190 80 0.6 20.6 150 Cu-0.5%Pd/SiO 2 9.39 99 96 2.5 200 100 0.5-300 Cu@CNTs 14.3 99 87 2.5 240 200 0.2-200 The TOF value of Cu/SiO 2 -MOF catalyst was calculated by the following equation according to ref 6. [Reaction conditions: T= 190 C, P= 2.0 MPa, H 2 /DMO molar ratio= 50, WLHSV DMO = 1.63 h -1, Conv. DMO = 17.2%] 2 8 10 3 6 11 12 TOF (h -1 ) = Conv. of DMO WLHSV DMO Molecular weight of DMO (mol g -catal -1 h -1 ) Numbers of Cu sites (mol g -catal -1 ) 11 / 13
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