Effect of Structural Ordering on the Performance of Mesoporous Carbon Supported CuCoCe Catalyst in the Synthesis of Higher Alcohols from Syngas†

doi:10.7503/cjcu20180207

Abstract

Abstract:

Three kinds of mesoporous carbons were synthesised via soft-templating methods by adjusting the molar ratio of formaldehyde and resorcinol in the carbon source. The CuCoCe catalysts supported on different mesoporous carbons were prepared by co-impregnation method. The effect of structural mesopore ordering to catalytic properties for higher alcohol synthesis from syngas was studied in this passage and the catalysts were characterized by X-ray diffraction(XRD), N₂ adsorption-desorption(BET), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS), etc. The results show that the catalytic property has been constantly improved with the improvement of mesopore ordering. The catalyst supported on the highly ordered mesoporous carbon has the highest space-time yield(869.14 mg· $g cat - 1$ ·h^-1) and selectivity(50.48%) of higher alcohols, where the mole fraction of C₂₊OH reached 90.31% in the alcohol products.This study show that the pore structure affects the distribution and presence of active metals on the support. Highly ordered 2D hexagonal straight pore channels are conducive to the uniform dispersion of the active component CuCo and its close association, which promot the electron transfer between the two, thereby effectively inhibiting the continuous growth of the carbon chain, resulting in a significant increase in the activity of the catalyst and narrowing the distribution of the alcohol product.

Key words: Ordered mesoporous carbon, Mesopore ordering, Syngas, Higher alcohol, CuCoCe catalyst

CLC Number:

O643

TrendMD:

WEI Junyi, GAO Zhihua, HUANG Wei, AI Peipei, YAN Feifei, YOU Xiangxuan. Effect of Structural Ordering on the Performance of Mesoporous Carbon Supported CuCoCe Catalyst in the Synthesis of Higher Alcohols from Syngas^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1741.

Figures/Tables 13

Fig.1 Small angel XRD patterns of the mesoporous carbons MC-1(a), MC-1.5(b) and MC-2(c)

Fig.2 TEM images of the mesoporous carbons MC-1.5(A, B), MC-1(C) and MC-2(D)

Fig.3 N2 adsorption-desorption isotherms and pore size distributions(insets) of the mesoporous carbons(A) and corresponding catalysts(B)(A) a. MC-1; b. MC-1.5; c. MC-2. (B) a. Cat-1; b. Cat-1.5; c. Cat-2.

Table 1 Structural and textural properties of the mesoporous carbons and corresponding catalysts

Sample	S_BET/(m²·g^-1)	Pore volume/(cm²·g^-1)	Most probable aperture/nm
MC-1	718	0.64	5.6
MC-1.5	745	0.76	5.6
MC-2	671	0.46	3.6
Cat-1	620	0.51	5.5
Cat-1.5	671	0.62	5.6
Cat-2	527	0.35	3.4

Fig.4 XRD patterns of the fresh catalysts Cat-1(a), Cat-1.5(b) and Cat-2(c)

Fig.5 TEM images of the fresh catalysts Cat-1(A, A'), Cat-1.5(B, B'), Cat-2(C, C') with different magnifications

Fig.6 Particle size distributions of the fresh catalysts Cat-1(A), Cat-1.5(B) and Cat-2(C)

Fig.7 H2-TPR profiles of the fresh catalysts Cat-1(a), Cat-1.5(b) and Cat-2(c)

Fig.8 SEM images(A1—C1) and EDS mapping(A2—A4, B2—B4, C2—C4) of the fresh catalysts Cat-1(A1—A4), Cat-1.5(B1—B4) and Cat-2(C1—C4)(A2—C2) Cu; (A3—C3) Co; (A4—C4) Ce.

Fig.9 Cu2p3/2 XPS(A) and Cu LMM Auger spectra(B) of the fresh catalysts Cat-1(a),Cat-1.5(b) and Cat-2(c)

Fig.10 Co2p(A) and Ce3d(B) XPS spectra of the fresh catalysts Cat-1(A), Cat-1.5(B) and Cat-2(C)

Table 2 Surface Cu, Co and Ce concentrations over fresh catalysts

Catalyst	Surface molar fraction(%)
Catalyst	Cu⁰	Cu⁺	Cu²⁺	Co³⁺	Co²⁺	Ce³⁺	Ce⁴⁺
Cat-1	27.4	15.3	57.3	50.7	49.3	31.0	69.0
Cat-1.5	40.0	16.5	43.5	61.6	38.4	34.6	65.4
Cat-2	29.4	11.9	58.6	51.3	48.7	31.6	68.4

Table 3 Catalytic performance of different catalysts for CO hydrogenation reaction*

Cat.	CO conv.(%)	Carbon selectivity (molar fraction of C, %)			STY_ROH/ (mg· $g cat - 1$ ·h^-1)	Alcohol distribution(molar fraction of C, %)
Cat.	CO conv.(%)	CO₂	ROH	CH	STY_ROH/ (mg· $g cat - 1$ ·h^-1)	MeOH	EtOH	PrOH	BuOH	PeOH	C₂₊OH
Cat-1	76.82	2.18	26.48	71.34	461.34	12.47	55.57	17.07	9.66	5.23	87.53
Cat-1.5	57.84	2.48	50.48	47.04	849.96	9.69	49.50	22.36	11.72	6.74	90.31
Cat-2	54.66	2.31	40.55	57.14	656.98	17.10	45.31	13.82	13.63	10.14	82.90

Table 3 Catalytic performance of different catalysts for CO hydrogenation reaction*

Cat.	CO conv.(%)	Carbon selectivity (molar fraction of C, %)			STY_ROH/ (mg· $g cat - 1$ ·h^-1)	Alcohol distribution(molar fraction of C, %)
Cat.	CO conv.(%)	CO₂	ROH	CH	STY_ROH/ (mg· $g cat - 1$ ·h^-1)	MeOH	EtOH	PrOH	BuOH	PeOH	C₂₊OH
Cat-1	76.82	2.18	26.48	71.34	461.34	12.47	55.57	17.07	9.66	5.23	87.53
Cat-1.5	57.84	2.48	50.48	47.04	849.96	9.69	49.50	22.36	11.72	6.74	90.31
Cat-2	54.66	2.31	40.55	57.14	656.98	17.10	45.31	13.82	13.63	10.14	82.90

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