金属掺杂对LaFe基钙钛矿催化CO<sub>2</sub>加氢制低碳烯烃性能影响

MA Li-hai; GAO Xin-hua; ZHANG Jian-li; MA Jing-jing; HU Xiu-de; GUO Qing-jie

doi:10.1016/S1872-5813(22)60063-X

金属掺杂对LaFe基钙钛矿催化CO₂加氢制低碳烯烃性能影响

doi: 10.1016/S1872-5813(22)60063-X

宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室化学化工学院, 宁夏银川 750021

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中图分类号: TQ546
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出版历程
- 收稿日期: 2022-05-30
- 修回日期: 2022-07-28
- 录用日期: 2022-07-31
- 网络出版日期: 2022-10-18
- 刊出日期: 2023-01-10

Effects of metal doping on the catalytic performance of LaFe-based perovskites for CO₂ hydrogenation to light olefins

State Key Laboratory of High-effciency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the Key Project of Natural Science Foundation of Ningxia (2022AAC02002) and the National Natural Science Foundation of China (U20A20124)

More Information

Corresponding author: E-mail: zhangjl@nxu.edu.cn; qingjie_guo@163.com

摘要

摘要: 通过溶胶-凝胶法和浸渍法制备K/LaFeBO₃ (B =Cu、Zr、Al、Mn、Ni、Zn)钙钛矿催化剂，结合SEM、XRD、BET、H₂-TPR、CO₂-TPD、TG、XPS等表征，探究了金属掺杂对LaFe基钙钛矿催化CO₂加氢制备低碳烯烃性能的影响。结果表明，Cu和Zn的加入有利于提高Fe分散度并降低还原温度，同时低温下氢的脱附增加且碱性位增多。氧空位迁移变化对催化活性和烯烃选择性有重要影响，当Cu和Zn在B位取代Fe时，氧迁移率增加明显，具有较低结合能的表面晶格氧富集，显著提高了催化活性，促进了低碳烯烃生成。
- 二氧化碳加氢 /
- 钙钛矿 /
- LaFeBO₃催化剂 /
- 氧迁移
Abstract: The catalytic behavior of K/LaFeBO₃ (B =Cu, Zr, Al, Mn, Ni, and Zn) perovskite catalysts prepared by sol-gel and impregnation methods was investigated for CO₂ hydrogenation to light olefins. The structure of various catalysts was characterized in detail by SEM, XRD, N₂ adsorption-desorption, H₂-TPR, CO₂-TPD, TG, and XPS analysis. With the addition of Cu and Zn, the particles size decreased with high dispersion of Fe, while the exposed basic sites increased with lower hydrogen desorption temperature. The oxygen mobility in perovskites exhibited a considerable impact on catalytic activity and olefins selectivity, which considerably increased when Fe was substituted by Cu and Zn at the B site. Olefins were formed preferentially from oxygen species of the surface lattice with low binding energies (BEs). In addition, a faster diffusion rate of oxygen would lead to an enrichment of lattice oxygen species on the surface and increase the production of olefins.
- CO₂ hydrogenation /
- perovskite /
- LaFeBO₃ catalyst /
- oxygen mobility

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Figure 1 Schematics of chemical looping coupled hydrogenation process

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Figure 2 XRD patterns of the calcined catalyst samples

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Figure 3 SEM images of LaFeO₃ ((a), (b)), LaFeMnO₃ (c), LaFeCuO₃ (d), LaFeAlO₃ (e), LaFeZrO₃ (f), LaFeZnO₃ (g) and LaFeNiO₃ (h)

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Figure 4 N₂ adsorption-desorption isotherms of various samples

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Figure 5 H₂-TPR profiles of the LaFeBO₃ samples

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Figure 6 CO₂-TPD profiles of the catalyst samples

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Figure 7 TG analysis of the catalyst samples

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Figure 8 Survey XPS profiles of LaFeBO₃ samples

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Figure 9 XPS spectra of O 1s for different samples

LaFeO₃(a), LaFeCuO₃(b), LaFeAlO₃(c), LaFeZrO₃(d), LaFeZnO₃(e), LaFeNiO₃(f), and LaFeMnO₃(g)

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Figure 10 XPS spectra of Fe 2p for different samples

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Table 1 Crystalline size of various catalyst samples

Catalyst	Crystalline size/nm^a	Lattice parameter/ Å
LaFeO₃	96	3.5628
LaFeMnO₃	14.8	3.8754
LaFeCuO₃	30.8	3.8903
LaFeAlO_3-	16.7	4.4676
LaFeZrO₃	22.8	3.6622
LaFeZnO₃	28.9	4.6819
LaFeNiO₃	29.8	6.4846
^a: Caculated by Scherrer equation

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Table 2 Texture properties of LaFeBO₃ catalyst samples

Catalyst^a	BET/ (m²·g⁻¹)^b	V_total/ (cm³·g⁻¹)	Average pore diameter^c/nm
LaFeO₃	11.5	0.118	40.96
LaFeMnO₃	27.5	0.108	15.68
LaFeCuO₃	3.8	0.023	24.83
LaFeAlO₃₋	2.1	0.014	26.74
LaFeZrO₃	3.4	0.011	12.55
LaFeZnO₃	4.2	0.010	9.58
LaFeNiO₃	9.5	0.071	29.80
a: Fresh samples, b: BET desorption cumulative volume, c: BET desorption average pore diameter

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Table 3 Surface composition of the catalysts determined by XPS

Sample	Surface element content w_mol/%			Fe/B	Fe/B*
Sample	Fe	O	B	Fe/B	Fe/B*
LaFeMnO₃	3.81	59.01	4.09	0.93	0.69
LaFeCuO₃	5.87	59.29	6.09	0.96	0.98
LaFeAlO₃	4.15	60.1	6.03	0.69	0.59
LaFeZrO₃	4.77	54.95	8.02	0.59	0.53
LaFeZnO₃	3.8	57.41	4.67	0.81	0.87
LaFeNiO₃	7.48	59.74	8.05	0.93	0.89
* Determined by ICP

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Table 4 Catalytic activity of different catalysts

Catalyst sample	CO₂ conv. /%	CO sel. /%	Hydrocarbon distribution C/%				O/P
Catalyst sample	CO₂ conv. /%	CO sel. /%	CH₄	${\rm{C} }_{2}^= - {\rm{C} }_{4}^=$	${\rm{C} }_{2}^{0} - {\rm{C} }_{4}^{0}$	C₅₊	O/P
K/LaFeO₃	5.6	24.2	90.4	0	9.6	0	0
K/LaFeMnO₃	25.3	85.0	51.6	19.3	15.1	14.1	1.3
K/LaFeCuO₃	35.6	62.3	41.3	27.2	22.7	8.8	1.2
K/LaFeZrO₃	7.4	81.5	77.8	14.1	8.1	0	1.5
K/LaFeAlO₃	8.2	87.6	78.9	10.0	11.1	0	0.9
K/LaFeNiO₃	30.3	80.3	69.9	10.9	9.3	10	1.2
K/LaFeZnO₃	48.5	25.7	15.62	41.0	16.9	26.5	2.4
Reaction conditions: H₂/CO₂ = 3, 320 °C, 2.0 MPa, 1000 h⁻¹ and TOS=24 h

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