Supporting Information. High-performance CoCu catalyst encapsulated in KIT-6 for higher. alcohol synthesis from syngas

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S1

Supporting Information

High-performance CoCu catalyst encapsulated in KIT-6 for higher

alcohol synthesis from syngas

Zhuoshi Li†_{, Zhuang Zeng}†_{, Dawei Yao}†_{, Siqi Fan}†_{, Shaoxia Guo}†_{, Jing Lv}*, †_, Shouying Huang†_{, Yue Wang}*, †_{, Xinbin Ma}†

†_{Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative}

Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin 300072, People’s

Republic of China

Corresponding authors:

E-mail: muddylj@tju.edu.cn (J. Lv), yuewang@tju.edu.cn (Y. Wang).

Number of pages: 16 Number of figures: 8 Number of tables: 5

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S2 CONTENT

Figure S1 The results of N2 adsorption-desorption experiments……….……... S3

Figure S2 Low-angle XRD patterns of KIT-6 and Co3Cu1/KIT-6………...…... S4

Figure S3 TEM results of the calcined Co3Cu1/KIT-6……….…... S5

Figure S4 Comparison between direct calcination and two-step pyrolysis……... S6 Figure S5 STEM image and EDX elemental mapping image ………..………….… S7 Figure S6 H2-TPR profiles of the calcined catalysts ...……….………….… S8

Figure S7 Peak-fitted XPS spectra of calcined catalysts ...……….…S9 Figure S8 Comparison of XPS spectra between reduced and used catalyst…..……S10 Table S1 Physicochemical properties of as-prepared materials……...………...…... S11 Table S2 Catalytic performances of some catalysts reported in references….….…. S12 Table S3 Peak analysis of H2-TPR profiles…….……….……...…... S13

Table S4 Phase analysis by XPS spectra of calcined catalysts…….………...…... S14 Table S5 Quantitative results of Co species………... S15 Reference………...…... S16

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Figure S1. (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves

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Figure S3. TEM image of the calcined Co3Cu1/KIT-6 catalyst and corresponding

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Figure S4. XRD patterns of Co3Cu1/KIT-6 catalyst via directly calcination or two-step pyrolysis.

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Figure S5. (a), (b) STEM image and corresponding EDX elemental mapping images of (c) Co and (D) Cu in reduced Co3Cu1/KIT-6 catalyst.

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Figure S8. Comparison of (a) Cu 2p, (b) Co 2p and (c) C 1s XPS spectra between reduced and used Co3Cu1/KIT-6 catalyst.

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S11

Table S1. Physicochemical properties of as-prepared materials

a_{Determined by ICP-OES.}b_{Determined by N}

2 adsorption-desorption experiments. c_{Determined by CO-chemisorption.}d_{Calculated from XRD patterns by using the}

Scherrer equation. e_{Determined by TEM.}

Metal loading

(wt.%)

Particle size of Co or CoCu species

(nm) Sample

Coa Cua

SBET

(m2_/g)b

Pore volume (cm3_/g)b

Pore size (nm)b

dc dd

Averag e particle

size (nm)e

KIT-6 - - 936 1.6 7.1 - -

-Co/KIT-6 33.1 - 232 0.4 6.3 - -

-Co4Cu1/KIT-6 23.5 6.1 198 0.3 6.3 3.9 3.5 3.8

Co3Cu1/KIT-6 23.0 8.9 286 0.4 6.6 4.4 3.6 4.3

Co2Cu1/KIT-6 18.9 12.7 358 0.5 6.6 4.3 3.6 4.5

Co1Cu1/KIT-6 12.8 19.1 336 0.6 6.5 5.3 5.0 5.5

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Table S2. CO conversion and alcohol selectivity in some representative catalysts reported in references

Selectivity (%) Catalyst T (K) P (MPa) GHSV (h-1₎

H₂/ CO

X_co (%)

HC CO2 ROH

STY C2+OH

(mmol/gcat/h) Ref.

Co2Cu1Nb0.2 493 6 3600 1.5 10.0 46.0 1.0 45.0 N/A 1

Co8Cu8Mn8/AC 493 3 500 2 58.3 54.7 5.2 40.1 10.5 2

Cu-Co/Al2O3/CNTs

503 3 3900 2 45.4 35.3 1.8 62.9 16.0 3

Co3Cu1-11%CNT 300 5 7000 2 26.5 45.2 5.1 49.7 9.6 4

CoCu/GE–LFO 300 3 3900 2 50.0 35.0 8.0 57.0 10.7 5

Co3Cu1/KIT-6 270 3 9000 2 83.3 38.4 1.8 59.8 39.7 This

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S13 Table S3. Peak analysis of H2-TPR profiles

Catalyst

α peak proportion

(%)

β peak proportion

(%)

γ peak proportion

(%)

δ peak proportion

(%)

β/(α+β+γ)

(%)

Co1Cu1 12.2 41.0 40.5 5.3 43.7

Co2Cu1 12.7 47.0 26.7 13.6 54.3

Co3Cu1 18.1 57.6 13.8 10.5 64.3

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Table S4. Phase analysis by XPS results of calcined catalysts

Phase proportion (molar %) a

Catalyst

CuO CuxCo3-xO4

Co1Cu1 70.2 29.8

Co2Cu1 54.5 45.5

Co3Cu1 38.5 61.5

Co4Cu1 45.8 54.2

a_{The relative proportion of each phase was calculated from the deconvolution results}

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S15 Table S5. Quantitative results of Co species

Catalyst CO uptake a

(μmol/g) Dispersion b (%)

SCoCu c

(m2_/g)

Co1Cu1 452 18.2 3.2

Co2Cu1 692 21.8 6.7

Co3Cu1 699 21.9 10.1

Co4Cu1 688 24.8 8.9

a _{Obtained from CO-chemisorption}

b _{Obtained from CO-chemisorption, referring to the dispersion of total cobalt species.} c _{Obtained from quantifying XRD patterns of reduced catalysts combined with}

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S16 REFERENCE:

1. Xiang, Y.; Barbosa, R.; Li, X.; Kruse, N. Ternary Cobalt-Copper-Nibium Catalysts for the Selective CO Hydrogenation to Higher Alcohols. ACS Catal. 2015, 5 (5), 2929-2934.

2. Pei, Y.; Jian, S.; Chen, Y.; Wang, C. Synthesis of Higher Alcohols by the Fischer– Tropsch Reaction over Activated Carbon Supported CoCuMn Catalysts. RSC Adv. 2015, 5 (93), 76330-76336.

3. Cao, A.; Liu, G.; Wang, L.; Liu, J.; Yue, Y.; Zhang, L.; Liu, Y. Growing Layered Double Hydroxides on CNTs and Their Catalytic Performance for Higher Alcohol Synthesis from Syngas. J. Mater. Sci. 2016, 51 (11), 5216-5231.

4. Dong, X.; Liang, X.-L.; Li, H.-Y.; Lin, G.-D.; Zhang, P.; Zhang, H.-B. Preparation and Characterization of Carbon Nanotube-Promoted Co–Cu Catalyst for Higher Alcohol Synthesis from Syngas. Catal. Today 2009, 147 (2), 158-165.

5. Niu, T.; Liu, G. L.; Chen, Y.; Yang, J.; Wu, J.; Cao, Y.; Liu, Y. Hydrothermal Synthesis of Graphene-LaFeO3 Composite Supported with Cu-Co Nanocatalyst for