In-Co二元金属氧化物上CO2催化加氢反应的选择性转变: 催化反应的机理和构效关系

doi:10.1016/S1872-2067(21)63870-6

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 862-876.DOI: 10.1016/S1872-2067(21)63870-6

In-Co二元金属氧化物上CO₂催化加氢反应的选择性转变: 催化反应的机理和构效关系

李龙泰^a^,^†, 杨彬^b^,^c^,^†, 高彪^a, 王逸夫^a, 张玲霞^b^,^c, 石原达已^d, 齐伟^e^,^f^,^*(), 郭利民^a^,^#()

^a华中科技大学环境科学与工程学院, 湖北武汉 430074, 中国
^b中国科学院大学杭州高等研究院, 化学与材料科学学院, 浙江杭州 310000, 中国
^c中国科学院上海陶瓷研究所, 高性能陶瓷与超细微结构国家重点实验室, 上海 200050, 中国
^d九州大学国际碳中性能源研究所, 福冈, 日本
^e华中科技大学化学与化工学院, 生物无机化学与材料学湖北省重点实验室, 湖北武汉 430074, 中国
^f华中科技大学电气工程学院, 先进电子工程与技术国家重点实验室, 湖北武汉 430074, 中国

收稿日期:2021-06-10 修回日期:2021-06-10 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: 齐伟,郭利民
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(21878116);湖北省自然科学基金(2019CFA070)

CO₂ hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship

Longtai Li^a^,^†, Bin Yang^b^,^c^,^†, Biao Gao^a, Yifu Wang^a, Lingxia Zhang^b^,^c, Tatsumi Ishihara^d, Wei Qi^e^,^f^,^*(), Limin Guo^a^,^#()

^aSchool of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^bChemistry and Material Science College, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310000, Zhejiang, China
^cState Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
^dInternational Institute for Carbon-Neutral Energy Research, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 8190395, Japan
^eHubei Key Laboratory of Bioinorganic Chemistry & Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^fState Key Laboratory of Advanced Electronic Engineering and Technology, School of Electrical and Electrical Engineering, Huazhong Universi-ty of Science and Technology, Wuhan 430074, Hubei, China

Received:2021-06-10 Revised:2021-06-10 Online:2022-03-18 Published:2022-02-18
Contact: Wei Qi, Limin Guo
About author:First author contact:
^† Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21878116);Natural Science Foundation of Hubei Province(2019CFA070)

摘要/Abstract

摘要：

采用催化加氢的方式将CO₂转化为甲醇, 既可以减少CO₂排放, 又制备了化学品, 该反应具有重要的研究意义. 氧化铟(In₂O₃)作为CO₂加氢制甲醇催化剂, 由于其较高的CO₂活化能力和甲醇选择性, 被科研工作者广泛研究. 其中, 将具有良好解离H₂能力的过渡金属元素引入In₂O₃(M/In₂O₃)是有效提高催化剂性能的策略之一, 然而, M/In₂O₃体系催化CO₂加氢反应机理及活性位点仍不清楚. 本文引入Co制备了In-Co二元金属氧化物催化剂应用于CO₂加氢制甲醇, 结果表明, 相较于In₂O₃, In-Co催化剂性能有很大提升, 其中In₁-Co₄催化剂上甲醇时空产率(9.7 mmol·g_cat^‒1 h^‒1)是In₂O₃(2.2 mmol·g_cat^‒1 h^‒1)的近5倍(反应条件: P = 4.0 MPa, T = 300 ^oC, GHSV = 24000 cm³_STP g_cat^‒1 h^‒1, H₂/CO₂ = 3). 值得注意的是, 尽管Co是金属元素的主体, In-Co催化剂中Co催化CO₂甲烷化的活性受到明显抑制. 本文还通过多种技术系统研究了催化剂结构与反应选择性转变间的关系.
采用电感耦合等离子体发射光谱、粉末X射线衍射、拉曼光谱、X射线光电子能谱和透射电子显微镜等对催化剂结构以及表面性质进行了表征. 结果表明, 在H₂还原气氛诱导下, In-Co催化剂表面发生重构, 形成以CoO为核, 以In₂O₃为壳的核壳结构, 其在高压反应后仍能保持稳定; 更重要的是, 该核壳结构可以显著增强In-Co催化剂吸附及活化CO₂的能力. CO₂加氢反应动力学研究表明, Co催化剂上H₂分压对CO₂加氢为零级反应, 而H₂分压在In-Co上的反应级数为正数; In-Co催化剂上, CO₂分压的反应级数接近于零, 表明CO₂及其衍生物在In-Co的表面吸附饱和, 但在纯Co上, 则不会发生这种饱和吸附.
通过原位DRIFTS研究了催化反应路径和关键中间物种的吸附及反应行为, 发现CO₂加氢在纯Co和In-Co上的催化机理均遵循甲酸盐路径. 在该催化路径中, CO₂首先加氢为甲酸盐(*HCOO)物种, 随后加氢为甲氧基(*CH₃O). *CH₃O在Co催化剂上进一步加氢生成CH₄, 而*CH₃O在In-Co催化剂上则会脱附生成CH₃OH. 根据表征结果, 本文认为, 在还原性气氛下, In-Co发生了重构并生成表面富In₂O₃的核壳状结构, 显著提高了催化剂对CO₂和含碳物种的吸附能力. Co和In-Co催化剂对CO₂加氢反应选择性的差异归因于催化剂对CO₂和对*HCOO等含碳中间物种的吸附稳定性不同. CO₂及其衍生的含碳中间物种在In-Co催化剂上的吸附能力比在Co催化剂上强, 形成了较合适的催化剂表面C/H比, 从而使*CH₃O能够脱附为CH₃OH, 而不是进一步加氢为CH₄. 综上, 本文研究为高活性In-Co催化剂体系在CO₂加氢反应中的催化机理及行为提供了解释, 为金属-氧化铟(M-In₂O₃)催化剂体系的设计提供了参考.

关键词: 氧化铟, 钴, CO₂加氢, 甲醇合成, 核壳结构, 表面C/H比

Abstract:

The hydrogenation of CO₂ into methanol has attracted much attention and In₂O₃ is a promising catalyst. Introducing metal elements into In₂O₃ (M/In₂O₃) is one of the main strategies to improve its performance. However, its mechanism and active sites remain unclear and need to be further elucidated. Here, the noble-metal-free In_x-Co_y oxides catalysts were prepared. Much-improved performance and obvious product selectivity shift were observed. The optimized catalyst (In₁-Co₄) (9.7 mmol g_cat^-1 h^-1) showed five times methanol yields than pure In₂O₃ (2.2 mmol g_cat^-1 h^-1) (P = 4.0 MPa, T = 300 °C, GHSV = 24000 cm³_STP g_cat^-1 h^-1, H₂:CO₂ = 3). And the cobalt-catalyzed CO₂ methanation activity was suppressed, although cobalt was most of the metal element. To unravel this selectivity shift, detailed catalysts performance evaluation, together with several in-situ and ex-situ characterizations, were employed on cobalt and In-Co for comparative study. The results indicated CO₂ hydrogenation on cobalt and In-Co catalyst both followed the formate pathway, and In-Co reconstructed and generated a surface In₂O₃-enriched core-shell-like structure under a reductive atmosphere. The enriched In₂O₃ at the surface significantly enhanced CO₂ adsorption capacity and well stabilized the intermediates of CO₂ hydrogenation. CO₂ and carbon-containing intermediates adsorbed much stronger on In-Co than cobalt led to a feasible surface C/H ratio, thus allowing the *CH₃O to desorb to produce CH₃OH instead of being over-hydrogenated to CH₄.

Key words: Indium oxide, Cobalt, CO₂ hydrogenation, Methanol synthesis, Core-shell structure, Surface C/H ratio

李龙泰, 杨彬, 高彪, 王逸夫, 张玲霞, 石原达已, 齐伟, 郭利民. In-Co二元金属氧化物上CO₂催化加氢反应的选择性转变: 催化反应的机理和构效关系[J]. 催化学报, 2022, 43(3): 862-876.

Longtai Li, Bin Yang, Biao Gao, Yifu Wang, Lingxia Zhang, Tatsumi Ishihara, Wei Qi, Limin Guo. CO₂ hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship[J]. Chinese Journal of Catalysis, 2022, 43(3): 862-876.

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图/表 14

Table 1 Physicochemical properties of as-prepared catalysts.

Catalyst	Indium element molar proportion (%) ^a	BET surface area (m² g^-1)	Crystallite size (nm)^b
Catalyst	Indium element molar proportion (%) ^a	BET surface area (m² g^-1)	Co₃O₄	In₂O₃
Co₃O₄	0	42.89	16.6	—
In₁-Co₁₉	4.8	52.15	12.3	—
In₁-Co₉	8.9	58.75	11.2	—
In₁-Co₄	19.5	71.88	5.7	—
In₁-Co₁	51.1	29.39	13.6	15.1
In₂O₃	100	28.61	—	18

Fig. 1. Morphological and structural characterizations of as-prepared catalysts. XRD patterns (a) and Raman spectra (b) of as-prepared Inx-Coy catalysts with different In/Co molar ratios versus the referential In2O3 and Co3O4 catalysts; TEM image (c) and high-resolution TEM image (d) of as-prepared In1-Co4; (e) HAADF-STEM image and corresponding EDS elemental mappings of as-prepared In1-Co4.

Fig. 2. Catalytic performances of the catalysts. (a) CO2 conversion, product selectivity; (b) CH3OH and CH4 yield of catalysts of Inx-Coy catalysts with different In/Co molar ratios versus the referential In2O3 and Co3O4 catalysts; (c) product selectivity of In1-Co4 by co-precipitation and physical-mixed methods; (d) product selectivity, CO2 conversion of In1-Co4 catalyst with different GHSV; (e,f) the comparison of catalytic performance between In1-Co4 and Co3O4 at different pressures or H2/CO2 feeding ratio conditions. Typical reaction conditions: P = 4.0 MPa, T = 300 °C, GHSV = 24000 cm3STP gcat-1 h-1, H2/CO2 = 3 (unless otherwise specified), all catalysts were reduced under 20% H2/Ar at 300 °C for 2 h before reaction.

Fig. 3. Comparative structural characterizations of as-prepared and reduced catalysts. (a) XRD patterns; (b) XPS spectroscopy with core level Co 2p, Raman spectra (c) of as-prepared and reduced In1-Co4 catalyst; (d) H2-TPR of as-prepared catalysts.

Fig. 4. Morphological and structural characterizations of the reduced catalysts. TEM image (a) and high-resolution TEM image (b) of the reduced In1-Co4; (c) EDS line scan profile of reduced In1-Co4.

Fig. 5. CO2 adsorption ability over different catalysts. (a) CO2-TPD profiles of reduced catalysts; (b) CO2 adsorption DRIFTS spectra of different catalysts at 25 °C; (c) CO2 adsorption DRIFTS spectra of In1-Co4 at different temperatures.

Table 2 Infrared band assignments of the surface species on catalysts.

Surface species	Wavenumber (cm^-1)	assignment	Ref.
CO₂	2358	ν(C=O)	[51]
CH₄	3018	ν(C-H)	[51]
Carbonate *CO₃	1330	ν_s(OCO)	[24,47,48]
Carbonate *CO₃	1583	ν_as(OCO)	[24,47,48]
Bicarbonate *HCO₃	1236	ν_s(OCO)	[24,47,48]
	1429	δ(CH)	[24,47,48]
	1626, 1656	ν_as(OCO)	[24,47,48]
Formate *HCOO	1347-1355	ν_s(OCO)	[24,48,50]
	1382	δ(CH)	[24,48,50]
	1578-1581, 1642-1645	ν_as(OCO)	[24,48,50]
	2867-2875	ν(CH)	[24,48,50]
	2735, 2957-2964	δ(CH) + ν (OCO)	[24,48,50]
Methoxyl *CH₃O	1045-1049	ν(CH) of terminal *CH₃O	[24,48,51]
Methoxyl *CH₃O	2820-2827, 2935-2942	ν(CH₃)	[24,48,51]
*CO	2077	adsorbed linear CO species	[24,47,48]
Gaseous HCOOH	1083	δ(CH)	[52,53]
	1214	ν(CO)	[52,53]
	1789	ν(C=O)	[52,53]
	2939-2943	ν(CH) + δ(CH)	[52,53]
Adsorbed HCOOH	1119	ν(CO)	[52,53]
Adsorbed HCOOH	1749	ν(C=O)	[52,53]

Fig. 6. Dependence of CO2 conversion rate towards H2 partial pressure and CO2 partial pressure over reduced Co3O4 (a) and In1-Co4 (b). Reaction conditions: P = 4.0 MPa, T = 300 °C, H2/CO2 = 3, more details are in the supplementary materials.

Fig. 7. In-situ DRIFTS spectra of the CO2 + H2 reaction after CO2 adsorption on reduced Co3O4 (a) and In1-Co4 (b). Reaction conditions: P = 0.1 MPa, T = 250 °C, 5 mL/min CO2 + 15 mL/min H2, all catalysts were reduced under 20% H2/Ar at 300 °C for 2 h before reaction.

Fig. 8. HCOOH/CH3OH adsorption DRIFTS spectra on reduced Co3O4 and In1-Co4. HCOOH adsorption DRIFTS spectra on reduced Co3O4 (a) and In1-Co4 (b) at different temperatures. CH3OH adsorption DRIFTS spectra on reduced Co3O4 (c) and In1-Co4 (d) at different temperatures. All spectra were collected after introducing HCOOH/CH3OH for 30 min to ensure adsorption saturation; all catalysts were reduced under 20% H2/Ar at 300 °C for 2 h before the adsorption process.

Fig. 9. In-situ DRIFTS spectra of H2 reaction after CH3OH saturated adsorbed on reduced In1-Co4 and Co3O4. Reaction conditions: P = 0.1 MPa, T = 250 °C, methanol was first bubbled in for 30 min then the gas was switched to 15 mL/min H2 for further reaction; all catalysts were reduced under 20% H2/Ar at 300 °C for 2 h before the adsorption process.

Scheme 1. CO2 hydrogenation pathways on reduced Co3O4 and Inx-Coy catalysts.

Table 3 Performance comparison of different In-Co catalysts.

Catalyst	P (MPa)	T (°C)	H₂/CO₂ ratio	GHSV (cm³_STP g_cat^-1 h^-1)	In/Co ratio	CO₂ Conversion (%)	Methanol Selectivity (%)	rate_MeOH (g g_cat^-1 h^-1)	Ref.
In@Co-2	5	300	4	27500	1	17	80	0.86	[12]
MOF-derived In₂O₃@Co₃O₄	5	300	4	16500	3/4	20.5	65	0.65	[37]
50% In₂O₃/Co/C-N	2	300	3	3000	—	9.5	88.4	0.08	[36]
In₁-Co₄	4	300	3	24000	1/4	8.9	46.5	0.31	this work
In₁-Co₉	4	300	3	24000	1/9	8.2	43.5	0.30	this work

Scheme 2. Schematic adsorption-selectivity relationship for reduced Co3O4 and Inx-Coy catalysts in CO2 hydrogenation reactions.

参考文献

[1]	J. T. Houghton, G. J. Jenkins, J. J. Ephraums, in: Climate Change: The IPCC assessment, Cambridge Univ. Press, U.K., 1990.
[2]	G. A. Olah, Angew. Chem. Int. Ed., 2005, 44, 2636-2639.
[3]	S. Kattel, P. Liu, J. G. Chen, J. Am. Chem. Soc., 2017, 139, 9739-9754.
[4]	P. Tian, Y. Wei, M. Ye, Z. Liu, ACS Catal., 2015, 5, 1922-1938.
[5]	H. Koempel, W. Liebner, Stud. Surf. Sci. Catal., 2007, 167, 261-267.
[6]	M. Bjørgen, F. Joensen, M. S. Holm, U. Olsbye, K.-P. Lillerud, S. Svelle, Appl. Catal. A, 2008, 345, 43-50.
[7]	J. A. Rodriguez, P. Liu, D. J. Stacchiola, S. D. Senanayake, M. G. White, J. G. Chen, ACS Catal., 2015, 5, 6696-6706.
[8]	K. Larmier, W. C. Liao, S. Tada, E. Lam, R. Verel, A. Bansode, A. Urakawa, A. Comas-Vives, C. Coperet, Angew. Chem. Int. Ed., 2017, 56, 2318-2323.
[9]	S. Li, Y. Wang, B. Yang, L. Guo, Appl. Catal. A, 2019, 571, 51-60.
[10]	B. Yang, W. Deng, L. Guo, T. Ishihara, Chin. J. Catal., 2020, 41, 1348-1359.
[11]	X. Jiang, Y. Jiao, C. Moran, X. Nie, Y. Gong, X. Guo, K.S. Walton, C. Song, Catal. Commun., 2019, 118, 10-14.
[12]	A. Bavykina, I. Yarulina, A. J. Al Abdulghani, L. Gevers, M. N. Hedhili, X. Miao, A. R. Galilea, A. Pustovarenko, A. Dikhtiarenko, A. Cadiau, A. Aguilar-Tapia, J. L. Hazemann, S. M. Kozlov, S. Oud-Chikh, L. Cavallo, J. Gascon, ACS Catal., 2019, 9, 6910-6918.
[13]	M. S. Frei, C. Mondelli, R. Garcia-Muelas, K. S. Kley, B. Puertolas, N. Lopez, O. V. Safonova, J. A. Stewart, D. Curulla Ferre, J. Perez-Ramirez, Nat. Commun., 2019, 10, 3377.
[14]	O. Martin, A. J. Martin, C. Mondelli, S. Mitchell, T. F. Segawa, R. Hauert, C. Drouilly, D. Curulla-Ferre, J. Perez-Ramirez, Angew. Chem. Int. Ed., 2016, 55, 6261-6265.
[15]	J. Ye, C. Liu, Q. Ge, J. Phys. Chem. C, 2012, 116, 7817-7825.
[16]	A. García-Trenco, A. Regoutz, E. R. White, D. J. Payne, M. S. P. Shaffer, C. K. Williams, Appl. Catal. B, 2018, 220, 9-18.
[17]	M. S. Frei, M. Capdevila-Cortada, R. García-Muelas, C. Mondelli, N. López, J. A. Stewart, D. Curulla Ferré, J. Pérez-Ramírez, J. Catal., 2018, 361, 313-321.
[18]	X. Jia, K. Sun, J. Wang, C. Shen, C. J. Liu, J. Energy Chem., 2020, 50, 409-415.
[19]	N. Rui, F. Zhang, K. Sun, Z. Liu, W. Xu, E. Stavitski, S. D. Senanayake, J. A. Rodriguez, C.-J. Liu, ACS Catal., 2020, 10, 11307-11317.
[20]	N. Rui, Z. Wang, K. Sun, J. Ye, Q. Ge, C. J. Liu, Appl. Catal. B, 2017, 218, 488-497.
[21]	T. Y. Chen, C. Cao, T. B. Chen, X. Ding, H. Huang, L. Shen, X. Cao, M. Zhu, J. Xu, J. Gao, Y. F. Han, ACS Catal., 2019, 9, 8785-8797.
[22]	A. Cao, Z. Wang, H. Li, J. K. Nørskov, ACS Catal., 2021, 11, 1780-1786.
[23]	J. Wang, G. Zhang, J. Zhu, X. Zhang, F. Ding, A. Zhang, X. Guo, C. Song, ACS Catal., 2021, 11, 1406-1423.
[24]	B. Yang, L. Li, Z. Jia, X. Liu, C. Zhang, L. Guo, Chin. Chem. Lett., 2020, 31, 2627-2633.
[25]	M. Behrens, F. Studt, I. Kasatkin, S. Kühl, M. Hävecker, F. Abild-Pedersen, S. Zander, F. Girgsdies, P. Kurr, B. L. Kniep, M. Tovar, R. W. Fischer, J. K. Norskov, R. Schloegl, Science, 2012, 336, 893-897.
[26]	J. T. Sun, I. S. Metcalfe, M. Sahibzada, Ind. Eng. Chem. Res., 1999, 38, 3868-3872.
[27]	J. Bao, G. Yang, Y. Yoneyama, N. Tsubaki, ACS Catal., 2019, 9, 3026-3053.
[28]	W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian, Q. Zhang, Y. Wang, Chem. Soc. Rev., 2019, 48, 3193-3228.
[29]	P. Gao, S. G. Li, X. N. Bu, S. S. Dang, Z. Y. Liu, H. Wang, L. S. Zhong, M. H. Qiu, C. G. Yang, J. Cai, W. Wei, Y. H. Sun, Nat. Chem., 2017, 9, 1019-1024.
[30]	S. Dang, P. Gao, Z. Liu, X. Chen, C. Yang, H. Wang, L. Zhong, S. Li, Y. Sun, J. Catal., 2018, 364, 382-393.
[31]	J. Ye, Q. Ge, C. J. Liu, Chem. Eng. Sci., 2015, 135, 193-201.
[32]	N. Dostagir, C. Thompson, H. Kobayashi, A. M. Karim, A. Fukuoka, A. Shrotri, Catal. Sci. Technol., 2020, 10, 8196-8202.
[33]	Z. Han, C. Tang, J. Wang, L. Li, C. Li, J. Catal., 2021, 394, 236-244.
[34]	Z. Shi, Q. Tan, C. Tian, Y. Pan, X. Sun, J. Zhang, D. Wu, J. Catal., 2019, 379, 78-89.
[35]	M. M. J. Li, H. Zou, J. Zheng, T. S. Wu, T. S. Chan, Y. L. Soo, X.P. Wu, X. Q. Gong, T. Chen, K. Roy, G. Held, S. C. E. Tsang, Angew. Chem. Int. Ed., 2020, 59, 16039-16046.
[36]	T. Fang, B. Liu, Y. Lian, Z. Zhang, Ind. Eng. Chem. Res., 2020, 59, 19162-19167.
[37]	A. Pustovarenko, A. Dikhtiarenko, A. Bavykina, L. Gevers, A. Ramírez, A. Russkikh, S. Telalovic, A. Aguilar, J. L. Hazemann, S. Ould-Chikh, J. Gascon, ACS Catal., 2020, 10, 5064-5076.
[38]	J. L. Snider, V. Streibel, M. A. Hubert, T. S. Choksi, E. Valle, D. C. Upham, J. Schumann, M. S. Duyar, A. Gallo, F. Abild-Pedersen, T. F. Jaramillo, ACS Catal., 2019, 9, 3399-3412.
[39]	J. Zhao, W. Han, J. Zhang, Z. Tang, Arab. J. Chem., 2020, 13, 4857-4867.
[40]	C. Yang, S. Liu, Y. Wang, J. Song, G. Wang, S. Wang, Z. J. Zhao, R. Mu, J. Gong, Angew. Chem. Int. Ed., 2019, 58, 11242-11247.
[41]	Y. Shen, J. Deng, S. Impeng, S. Li, T. Yan, J. Zhang, L. Shi, D. Zhang, Environ. Sci. Technol., 2020, 54, 10342-10350.
[42]	J. Díez-Ramírez, P. Sánchez, V. Kyriakou, S. Zafeiratos, G.E. Marnellos, M. Konsolakis, F. Dorado, J. CO₂ Utili., 2017, 21, 562-571.
[43]	S. Kattel, P. J. Ramírez, J. G. Chen, J. A. Rodriguez, P. Liu, Science, 2017, 355, 1296-1299.
[44]	B. Rivas-Murias, V. Salgueiriño, J. Raman Spectro., 2017, 48, 837-841.
[45]	C. W. Tang, C. B. Wang, S. H. Chien, Thermochim. Acta, 2008, 473, 68-73.
[46]	W. Li, G. Zhang, X. Jiang, Y. Liu, J. Zhu, F. Ding, Z. Liu, X. Guo, C. Song, ACS Catal., 2019, 9, 2739-2751.
[47]	F. Liao, Y. Huang, J. Ge, W. Zheng, K. Tedsree, P. Collier, X. Hong, S. C. Tsang, Angew. Chem. Int. Ed., 2011, 50, 2162-2165.
[48]	S. Kattel, B. Yan, Y. Yang, J. G. Chen, P. Liu, J. Am. Chem. Soc., 2016, 138, 12440-12450.
[49]	T. Bielz, H. Lorenz, W. Jochum, R. Kaindl, F. Klauser, B. Klotzer, S. Penner, J. Phys. Chem. C, 2010, 114, 9022-9029.
[50]	J. Wang, G. Li, Z. Li, C. Tang, Z. Feng, H. An, H. Liu, T. Liu, C. Li, Sci. Adv., 2017, 3, e1701290.
[51]	S. Kattel, W. Yu, X. Yang, B. Yan, Y. Huang, W. Wan, P. Liu, J. G. Chen, Angew. Chem. Int. Ed., 2016, 55, 7968-7973.
[52]	T. Chen, G. Wu, Z. Feng, G. Hu, W. Su, P. Ying, C. Li, Chin. J. Catal., 2008, 29, 105-107.
[53]	J. Raskó, T. Kecskés, J. Kiss, J. Catal., 2004, 224, 261-268.
[54]	J. J. Sims, C. A. Ould Hamou, R. Réocreux, C. Michel, J. B. Giorgi, J. Phys. Chem. C, 2018, 122, 20279-20288.
[55]	P. A. U. Aldana, F. Ocampo, K. Kobl, B. Louis, F. Thibault-Starzyk, M. Daturi, P. Bazin, S. Thomas, A. C. Roger, Catal. Today, 2013, 215, 201-207.
[56]	C. Yuan, N. Yao, X. Wang, J. Wang, D. Lv, X. Li, Chem. Eng. J., 2015, 260, 1-10.
[57]	Q. Pan, J. Peng, S. Wang, S. Wang,, Catal. Sci. Technol., 2014, 4, 502-509.
[58]	V. Navarro, M. A. van Spronsen, J. W. M. Frenken, Nat. Chem., 2016, 8, 929-934.
[59]	Y. Dai, F. Yu, Z. Li, Y. An, T. Lin, Y. Yang, L. Zhong, H. Wang, Y. Sun, Chin. J. Chem., 2017, 35, 918-926.
[60]	C. G. Visconti, L. Lietti, E. Tronconi, P. Forzatti, R. Zennaro, E. Finocchio, Appl. Catal. A, 2009, 355, 61-68.
[61]	Y. Zhang, G. Jacobs, D. E. Sparks, M.E. Dry, B.H. Davis, Catal. Today, 2002, 71, 411-418.
[62]	M. K. Gnanamani, G. Jacobs, R. A. Keogh, W. D. Shafer, D. E. Sparks, S. D. Hopps, G. A. Thomas, B. H. Davis, Appl. Catal. A, 2015, 499, 39-46.
[63]	G. Melaet, W. T. Ralston, C. S. Li, S. Alayoglu, K. An, N. Musselwhite, B. Kalkan, G. A. Somorjai, J. Am. Chem. Soc., 2014, 136, 2260-2263.
[64]	C. G. Visconti, M. Martinelli, L. Falbo, L. Fratalocchi, L. Lietti, Catal. Today, 2016, 277, 161-170.

In-Co二元金属氧化物上CO₂催化加氢反应的选择性转变: 催化反应的机理和构效关系

CO₂ hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship

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