Effects of sodium on the catalytic performance of CoMn catalysts for Fischer-Tropsch to olefins
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1 Supporting Information Effects of sodium on the catalytic performance of CoMn catalysts for Fischer-Tropsch to olefins Zhengjia Li a,b, Liangshu Zhong b,*, Fei Yu b,c, Yunlei An b,d, Yuanyuan Dai b,c, Yanzhang Yang b,c, Tiejun Lin b, Shenggang Li b,e, Hui Wang b, Peng Gao b, Yuhan Sun b,e,*, Mingyuan He a a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai , PR China. b CAS Key Laboratory of Low-carbon Conversion Science & Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai , PR China c University of the Chinese Academy of Sciences, Beijing , PR China d School of Environmental and Chemical Engineering, Shanghai University, Shanghai , PR China e School of Physical Science and Technology, ShanghaiTech University, Shanghai , PR China Corresponding Authors * for L. S. Zhong: zhongls@sari.ac.cn * for Y. H. Sun: sunyh@sari.ac.cn S1
2 Table of Contents Table S1: Elemental analysis s3 Table S2: Textural properties...s3 Table S3: Catalytic performance..s4 Table S4: Catalytic performance......s4 Table S5: Catalytic performance......s5 Figure S1: Mass spectra......s6 Figure S2: TEM images of the reduced catalysts. S7 Figure S3: Peak fitting of the XRD patterns....s8 Figure S4: Stability of Co 2 C nanoprisms.....s9 Figure S5: Catalytic performance s10 Figure S6: Products distributions... S11 Figure S7: XRD patterns of the spent catalysts.....s11 Figure S8: TEM images of the spent catalysts...s12 S2
3 Table S1. Elemental analysis of the calcined CoMn catalysts with different Na concentrations. Sample Sodium concentrations (wt.%) a Sodium concentrations (wt.%) b Co/Mn b CoMn-0Na CoMn-0.1Na CoMn-0.2Na CoMn-0.4Na CoMn-0.6Na a Nominal loadings, b Atomic ratio measured with ICP Table S2. Textural properties of the CoMn catalysts with different Na concentrations. Sample BET Surface Area (m 2 /g) Pore Volume (cm 3 /g) Pore Diameter (nm) Reduced Spent Reduced Spent Reduced Spent CoMn-0Na CoMn-0.1Na CoMn-0.2Na CoMn-0.4Na CoMn-0.6Na S3
4 Temperature ( o C) Table S3. Catalytic performance of the CoMn-0Na catalyst at different reaction temperatures. CO 2 Product Selectivity (C%, CO 2 -free) O/P Ratios CO Conv. Sele. = = = = (C%) CH (C%) 4 C 2 C 3 C 4 C 2-4 C 5+ + Oxy. C 2 C 3 C 4 C Table S4. Repeated study for the catalytic performance of the CoMn catalysts with different Na concentrations at 250 o C, 1 bar, GHSV=3000 ml/(h g cat ) and H 2 /CO=2. Sample Round CO 2 Product Selectivity (C%, CO 2 -free) O/P Ratios CO Conv. Sele. = = = = C%) CH (C%) 4 C 2 C 3 C 4 C 2-4 C 5+ + Oxy. C 2 C 3 C 4 C 2-4 CoMn-0Na CoMn-0.1Na CoMn-0.2Na CoMn-0.4Na CoMn-0.6Na S4
5 Table S5. Catalytic performance of the CoMn catalysts with different alkali promoter at 250 o C, 1 bar, GHSV=3000 ml/(h g cat ) and H 2 /CO=2. CO CO 2 Product Selectivity (C%, CO 2 -free) O/P Ratios Sample Conv. Sele. (C%) (C%) CH 4 = C 2 = C 3 = C 4 = C 2-4 C 5+ + Oxy. C 2 C 3 C 4 C 2-4 CoMn-0Na CoMn-0.4Li CoMn-0.4Na CoMn-0.4K CoMn-0.4Rb S5
6 Figure S1. Mass spectra of the calcined CoMn catalysts. S6
7 Figure S2. TEM images and particle size distributions for various reduced CoMn catalysts. (a) CoMn-0Na, (b) CoMn-0.1Na, (c) CoMn-0.2Na, (d) CoMn-0.4Na, (e) CoMn-0.6Na. S7
8 Figure S3. Peak fitting results of the spent CoMn catalysts with different Na concentrations based on step scanning patterns. (a) CoMn-0Na, (b) CoMn-0.1Na, (c) CoMn-0.2Na, (d) CoMn-0.4Na, (e) CoMn-0.6Na, (f) the relative content of Co and Co 2 C changing with Na concentrations. S8
9 Figure S4. XRD patterns, Co 2 C contents and TEM images of the spent CoMn-0.4Na catalysts after 50 and 100 hours of reaction, (a) XRD patterns, (b) Co 2 C contents, (c, d) 50 h, (e, f) 100 h. S9
10 Figure S5. Catalytic performance of the CoMn catalysts with different Na concentrations at 250 o C, 1 bar, H 2 /CO=2 and similar CO conversion (~20 C%). (a) CO conversion, (b) CO 2 selectivity, (c) product selectivity, (d) lower olefin selectivity, (e) O/P ratios of C 2-4, (f) product distribution. The GHSV for the CoMn-0Na, CoMn-0.1Na, CoMn-0.2Na, CoMn-0.4Na and CoMn-0.6Na catalysts were 7000, 6000, 5000, 3000 and 750 ml/(h g cat ), respectively. S10
11 Figure S6. Product distributions of the CoMn catalysts with different alkali promoters. Figure S7. XRD patterns of the spent CoMn catalysts with different alkali promoters. S11
12 Figure S8. TEM images of the spent CoMn catalysts with different alkali promoters. (a) CoMn-0Na, (b) CoMn-0.4Li, (c) CoMn-0.4Na, (d) CoMn-0.4K, (e) CoMn-0.4Rb. The nanoparticles marked by red circles and rectangles were in the shape of nanosphere and nanoprism, respectively. S12
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