ZnxZrO催化剂上协同位点用于乙烷C-H键靶向性断裂及CO2活化

doi:10.1016/S1872-2067(24)60235-4

催化学报 ›› 2025, Vol. 70: 272-284.DOI: 10.1016/S1872-2067(24)60235-4

Zn_xZrO催化剂上协同位点用于乙烷C-H键靶向性断裂及CO₂活化

强文军^a^,¹, 廖多华^a^,¹, 王茂林^b, 曾令真^b, 李伟奇^a, 马雪冬^a, 杨亮^a, 李爽^a^,^*(), 马丁^b^,^*()

^a西北大学化工学院, 陕西西安 710069
^b北京大学化学与分子工程学院, 北京分子科学国家实验室, 北京 100871

收稿日期:2024-10-15 接受日期:2025-01-05 出版日期:2025-03-18 发布日期:2025-03-20
通讯作者: * 电子信箱: shuangli722@126.com (李爽),dma@pku.edu.cn (马丁).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(21878244);国家自然科学基金(22472130);太原理工大学煤炭清洁高效利用国家重点实验室基金(MJNYSKL202407)

Synergistic sites over the Zn_xZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO₂ activation

Wenjun Qiang^a^,¹, Duohua Liao^a^,¹, Maolin Wang^b, Lingzhen Zeng^b, Weiqi Li^a, Xuedong Ma^a, Liang Yang^a, Shuang Li^a^,^*(), Ding Ma^b^,^*()

^aSchool of Chemical Engineering, Northwest University, Xi’an 710069, Shaanxi, China
^bBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2024-10-15 Accepted:2025-01-05 Online:2025-03-18 Published:2025-03-20
Contact: * E-mail: shuangli722@126.com (S. Li),dma@pku.edu.cn (D. Ma).
About author:¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21878244);National Natural Science Foundation of China(22472130);State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology(MJNYSKL202407)

摘要/Abstract

摘要：

CO₂辅助乙烷氧化脱氢(CO₂-ODHE)是将低碳烷烃(乙烷)和温室气体CO₂进行一体化资源利用的绿色工程, 具有重要意义. 该技术为碳资源有效利用、重要化工产品生产以及环境保护等提供了新的发展思路. 然而, 乙烷C-C/C-H键竞争性断裂仍然是研制高性能催化剂的重大挑战. 工业上主要通过乙烷蒸汽裂解和催化裂化生产乙烯, 但存在能耗高、碳排放大、结焦严重等缺点. 利用CO₂作为温和氧化剂, 选择性氧化乙烷脱氢制乙烯, 是更为原子经济性的反应, 并得到了工业界和学术界的广泛关注. 然而, 乙烷和CO₂转化率以及烯烃的选择性强烈依赖催化剂的组成和结构, 目前普遍存在活性有限、选择性不高、稳定性不够理想的问题. 合理设计催化剂是实现C-H键选择性剪裁和高效活化CO₂的关键.

本文采用沉积-沉淀法制备了一系列ZnO掺杂ZrO₂双功能催化剂(Zn_xZrO), 并通过原位表征和乙烷脉冲实验揭示了CO₂-ODHE反应重要的表面化学过程. X射线衍射、拉曼光谱、X射线吸收近边结构、X射线光电子能谱及二氧化碳程序升温脱附结果表明, ZrO₂中掺杂Zn²⁺后形成了Zn-O-Zr位点以及产生了更多氧空位(O_V). 通过原位红外及乙烷脉冲实验揭示了两种类型活性位点的功能: 中等强度Lewis酸性位点(Zn-O-Zr位点)选择性地断裂乙烷C-H键, 而强Brönsted碱性位点(氧空位)有效地激活CO₂ C=O键. 在Zn_xZrO催化剂上, CO₂-ODHE主要遵循乙烷脱氢和RWGS串联反应机理. 即乙烷在Zn-O-Zr位点直接脱氢生成C₂H₄和副产物H; 接着, CO₂与副产物H在氧空位上反应生成甲酸中间体, 甲酸中间体进一步解离成CO和H₂O, 同时Zn-O-Zr活性位点再生完成整个反应循环. 在性能测试方面, Zn_0.2ZrO催化剂表现出最佳的催化活性, 在5 h内平均C₂H₆转化率, C₂H₄产率和CO₂转化率分别达到19.1%, 10.5%和10.6% (600 °C, GHSV = 3000 mL/(g·h)). 尤其当GHSV增加至6000 mL/(g·h)时, 乙烯初始时空产率为355.5 μmol/(min·g).

综上所述, 本工作不仅为设计和研制廉价、高活性、高稳定性的催化剂提供依据和理论指导，助力实现CO₂利用的“闭路循环”, 而且为靶向性地裁剪C-H键生成烯烃提供了一种催化剂设计思路.

关键词: Zn-O-Zr位点, 氧空位, CO₂, 乙烯时空产率, 串联反应

Abstract:

The CO₂-assisted oxidative dehydrogenation of ethane (CO₂-ODHE) provides a promising way to produce ethylene and utilize CO₂. Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO₂ emissions could be achieved. However, the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts. In this paper, ZnO-doped ZrO₂ bifunctional catalysts (Zn_xZrO) with different Zn/Zr molar ratios were prepared by the deposition-precipitation method, and the functions of various sites for CO₂-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment: the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene, while the more oxygen vacancies (O_V) created by the introduction of Zn²⁺ are responsible for the efficient activation C=O bonds of CO₂, thus promoting the RWGS reaction. In addition, the Zn_0.2ZrO catalyst demonstrated excellent catalytic performances, with C₂H₆ conversion, C₂H₄ yield, and CO₂ conversion about 19.1%, 10.5%, and 10.6% within 5 h, respectively (600 °C, GHSV = 3000 mL/(g·h)). Especially, the initial ethylene space-time yield of 355.5 μmol/(min·g) was obtained under 6000 mL/(g·h); Finally, the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.

Key words: Zn-O-Zr site, Oxygen vacancies, CO₂, Ethylene space-time yield, Tandem reaction

强文军, 廖多华, 王茂林, 曾令真, 李伟奇, 马雪冬, 杨亮, 李爽, 马丁. Zn_xZrO催化剂上协同位点用于乙烷C-H键靶向性断裂及CO₂活化[J]. 催化学报, 2025, 70: 272-284.

Wenjun Qiang, Duohua Liao, Maolin Wang, Lingzhen Zeng, Weiqi Li, Xuedong Ma, Liang Yang, Shuang Li, Ding Ma. Synergistic sites over the Zn_xZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO₂ activation[J]. Chinese Journal of Catalysis, 2025, 70: 272-284.

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图/表 15

Fig. 1. The proposed reaction mechanism of CO2-ODHE over the ZnxZrO catalysts.

Fig. 2. (a) XRD patterns of ZrO2, ZnO, and ZnxZrO catalysts. (b) The partially enlarged XRD patterns of ZrO2, ZnO, and ZnxZrO catalysts. (c) Raman spectra of ZrO2, ZnO, and ZnxZrO catalysts.

Table 1 Crystal structures, the ZrO2 lattice parameters, cell volume, average grain size, and relative concentration of OV for ZrO2, ZnO, and ZnxZrO catalysts.

Catalyst	Crystal structure	ZrO₂ lattice parameter ^a		Cell volume ^a (Å^3)	Average grain size ^a (nm)	I₅₈₂/I₄₃₈ ^b
Catalyst	Crystal structure	a (Å)	c (Å)	Cell volume ^a (Å^3)	Average grain size ^a (nm)	I₅₈₂/I₄₃₈ ^b
ZrO₂	t-ZrO₂/m-ZrO₂	3.5931	5.1309	67.01	12	-
Zn_0.02ZrO	t-ZrO₂	3.5987	5.1140	66.77	17	0.27
Zn_0.05ZrO	t-ZrO₂	3.6004	5.1098	66.50	19	0.37
Zn_0.1ZrO	t-ZrO₂	3.6013	5.1089	66.42	23	0.42
Zn_0.2ZrO	t-ZrO₂	3.5926	5.0935	66.33	27	0.53
Zn₁ZrO	t-ZrO₂/h-ZnO	3.5982	5.2506	67.29	40	0.44
ZnO	h-ZnO	3.2491	5.2048	47.58	>100	0.34

Fig. 3. HRTEM images of ZrO2, ZnO, and ZnxZrO catalysts. (a,b) ZrO2; (c,d) Zn0.02ZrO; (e,f) Zn0.05ZrO; (g,h) Zn0.1ZrO; (i,j) Zn0.2ZrO; (k-n) Zn1ZrO; (o,p) ZnO.

Fig. 4. Zn K-edge XANES (a) and phase-uncorrected FT-EXAFS (b) spectra of Zn foil, ZnO, and ZnxZrO catalysts (The EXAFS spectra have been obtained by transforming the corresponding k3 χ(k) EXAFS function).

Fig. 5. XPS spectra of ZrO2, ZnO, and ZnxZrO catalysts. (a) Zr 3d; (b) Zn 2p; (c) O 1s.

Fig. 6. CO2-TPD profiles (a), Py-IR spectra after desorption at 200 °C (b) and NH3-TPD profiles (c) of ZnO, ZrO2, and ZnxZrO catalysts.

Table 2 The acid-base properties of ZrO2 and ZnxZrO catalysts.

Catalyst	The type of basic sites ^a (mmol/g)			The type of acid sites ^b (mmol/g)
Catalyst	Weak	Strong	Total	Weak	Medium	Strong
ZrO₂	0.1012	0.1142	0.2154	0.0433	0.0425	0.0768
Zn_0.02ZrO	0.0782	0.1224	0.2006	0.0387	0.0494	0.0729
Zn_0.05ZrO	0.0459	0.1377	0.1837	0.0243	0.0509	0.0649
Zn_0.1ZrO	0.0316	0.1441	0.1757	0.0156	0.0709	0.0521
Zn_0.2ZrO	0.0191	0.1501	0.1692	0.0195	0.0771	0.0483
Zn₁ZrO	0.0093	0.1237	0.1316	0.0223	0.0520	0.0382

Fig. 7. C2H6 conversion (a), C2H4 yield (b), and C2H4 selectivity and CO2 conversion (c) over ZrO2, ZnO, and ZnxZrO catalysts. Reaction conditions: T = 600 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 8. (a) XRD patterns of fresh and spent Zn0.2ZrO catalysts. (b) TG diagram of spent Zn0.2ZrO catalysts.

Fig. 9. XPS spectra of fresh and spent Zn0.2ZrO catalysts. (a) Survey; (b) Zr 3d; (c) Zn 2p; (d) O 1s.

Fig. 10. (a) The C2H6 conversion, C2H4 selectivity, and C2H4 STY over Zn0.2ZrO catalyst compared with other catalysts reported in the literature. Reaction conditions: T = 600 or 700 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h), Reference numbers were marked along with symbols. (b) The apparent activation energy of Zn0.2ZrO and other catalysts reported in the literature. Reaction conditions: T = 550, 575, 600, and 700 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 11. (a) Raman spectra of Zn0.2ZrO pretreated with CO at 500 and 600 °C. (b,c) XPS spectra of Zn0.2ZrO pretreated with HNO3 solution. C2H6 conversion and C2H4 yield over Zn0.2ZrO: pretreated with CO at 500 and 600 °C (d) and pretreated with HNO3 solution (e). Reaction conditions: T = 600 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 12. In situ FTIR spectra of reaction intermediates over the Zn0.2ZrO catalyst. (a) C2H6:N2 = 1:3; (b) CO2:N2 = 1:3; (c) C2H6:CO2:N2 = 1:1:2. Reaction conditions: T = 300 °C, GHSV = 12000 mL/(g·h)). α: HCOO*, HCO3*, and H3CO* stretching vibrations [76]; β: O-H stretching vibrations and gas CO2 stretching vibrations; γ: C-H and C=C stretching vibrations (ethylene); δ: C-H stretching vibrations (ethane) [77]; λ: C=O stretching vibrations (CO2) [78]; ε: HCOO* stretching vibrations [28].

Fig. 13. C2H6 Conversion (a) and C2H4 selectivity (b) over Zn0.2ZrO catalyst in C2H6 pulse experiment. Reaction conditions: T = 600 °C, C2H6:N2 = 1:3, GHSVC2H6 = 3000 mL/(g·h).

参考文献

[1]	R. Chauhan, R. Sartape, N. Minocha, I. Goyal, M. R. Singh, Energy Fuels, 2023, 37, 12589-12622.
[2]	M. Zhang, Y. Yu, Ind. Eng. Chem. Res., 2013, 52, 9505-9514.
[3]	Y. C. Li, L. Y. Li, S. Z. Luo, X. B. Huang, J. Shen, C. F. Jiang, F. L. Jing, Adv. Compos. Hybrid Mater., 2021, 4, 793-805.
[4]	D. Melzer, P. Xu, D. Hartmann, Y. Zhu, N. D. Browning, M. Sanchez-Sanchez, J. A. Lercher, Angew. Chem. Int. Ed., 2016, 55, 8873-8877.
[5]	X. Li, Y. Zhou, B. Qiao, X. Pan, C. Wang, L. Cao, L. Li, J. Lin, X. Wang, J. Energy Chem., 2020, 51, 14-20.
[6]	Y. Zhou, F. Wei, J. Lin, L. Li, X. Li, H. Qi, X. Pan, X. Liu, C. Huang, S. Lin, X. Wang, ACS Catal., 2020, 10, 7619-7629.
[7]	M. A. Artsiusheuski, R. Verel, J. A. van Bokhoven, V. L. Sushkevich, Angew. Chem. Int. Ed., 2023, 62, e202309180.
[8]	Y. F. Song, L. Lin, W. C. Feng, X. M. Zhang, Q. Dong, X. B. Li, H. F. Lv, Q. X. Liu, F. Yang, Z. Liu, G. X. Wang, X. H. Bao, Angew. Chem. Int. Ed., 2019, 58, 16043-16046.
[9]	L. T. Ye, X. Y. Duan, K. Xie, Angew. Chem. Int. Ed., 2021, 60, 21746-21750.
[10]	E. Gomez, B. Yan, S. Kattel, J. G. Chen, Nat. Rev. Chem., 2019, 3, 638-649.
[11]	S. Yao, B. Yan, Z. Jiang, Z. Liu, Q. Wu, J. H. Lee, J. G. Chen, ACS Catal., 2018, 8, 5374-5381.
[12]	A. Al-Mamoori, S. Lawson, A. A. Rownaghi, F. Rezaei, Appl. Catal. B, 2020, 278, 119329.
[13]	A. Al-Mamoori, T. Alghamdi, A. A. Rownaghi, F. Rezaei, Energy Fuels, 2020, 34, 14483-14492.
[14]	B. Yan, S. Yao, S. Kattel, Q. Wu, Z. Xie, E. Gomez, P. Liu, D. Su, J. G. Chen, Proc. Natl. Acad. Sci. U. S. A., 2018, 115, 8278-8283.
[15]	M. D. Porosoff, M. Myint, S. Kattel, Z. H. Xie, E. Gomez, P. Liu, J. G. Chen, Angew. Chem. Int. Ed., 2015, 54, 15501-15505.
[16]	X. Li, Z. Yang, L. Zhang, Z. He, R. Fang, Z. Wang, Y. Yan, J. Ran, Energy, 2021, 234, 121261.
[17]	M. Numan, E. Eom, A. Li, M. Mazur, H. W. Cha, H. C. Ham, C. Jo, S. E. Park, ACS Catal., 2021, 11, 9221-9232.
[18]	X. Wang, Y. Wang, B. Robinson, Q. Wang, J. Hu, J. Catal., 2022, 413, 138-149.
[19]	G. M. Li, C. Liu, X. J. Cui, Y. H. Yang, F. Shi, Green Chem., 2021, 23, 689-707.
[20]	T. A. Bugrova, V. V. Dutov, V. A. Svetlichnyi, V. Cortés Corberán, G. V. Mamontov, Catal. Today, 2019, 333, 71-80.
[21]	X. Li, S. Liu, H. Chen, S. Luo, F. Jing, W. Chu, ACS Omega, 2019, 4, 22562-22573.
[22]	J. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, B. M. Weckhuysen, Chem. Rev., 2014, 114, 10613-10653.
[23]	L. Li, R. Tan, S. Luo, C. Jiang, F. Jing, Appl. Catal. A, 2022, 635, 118565.
[24]	F. Cancino-Trejo, V. Santes, J. A. A. Cardenas, M. Gallardo, Y. G. Maldonado, L. Miranda A, O. Valdes, J. A. de los Reyes, C. E. Santolalla-Vargas, Chem. Eng. J. Adv., 2022, 12, 100404.
[25]	M. Guo, K. Feng, Y. Wang, B. Yan, ChemCatChem, 2021, 13, 3119-3131.
[26]	F. Xiao, D. Guo, F. Zhao, Y. Zhao, S. Wang, X. Ma, Asia-Pac. J. Chem. Eng., 2022, 17, e2804.
[27]	H. Guo, H. He, C. Miao, W. Hua, Y. Yue, Z. Gao, Mol. Catal., 2022, 519, 112155.
[28]	J. Liu, N. He, Z. Zhang, J. Yang, X. Jiang, Z. Zhang, J. Su, M. Shu, R. Si, G. Xiong, H. Xie, G. Vilé, ACS Catal., 2021, 11, 2819-2830.
[29]	J. Liu, Z. Zhang, Y. Jiang, X. Jiang, N. He, S. Yan, P. Guo, G. Xiong, J. Su, G. Vilé, Appl. Catal. B, 2022, 304, 120947.
[30]	Y. Chai, S. Chen, Y. Chen, F. Wei, L. Cao, J. Lin, L. Li, X. Liu, S. Lin, X. Wang, T. Zhang, J. Am. Chem. Soc., 2024, 146, 263-273.
[31]	Y. Liu, C. J. Xia, Q. Wang, L. Zhang, A. Huang, M. Ke, Z. Z. Song, Catal. Sci. Technol., 2018, 8, 4916-4924.
[32]	X. Li, Z. Yang, L. Zhang, Z. He, Y. Yan, J. Ran, Z. C. Kadirova, Fuel, 2022, 322, 124122.
[33]	Z. Feng, C. Tang, P. Zhang, K. Li, G. Li, J. Wang, Z. Feng, C. Li, J. Am. Chem. Soc., 2023, 145, 12663-12672.
[34]	D. H. Liao, L. Yang, G. Z. Song, X. D. Ma, S. Li, J. Fuel Chem. Technol., 2023, 51, 1421-1431.
[35]	B. Neppolian, Q. Wang, H. Yamashita, H. Choi, Appl. Catal. A, 2007, 333, 264-271.
[36]	D. Jevapatarakul, J. T-Thienprasert, S. Payungporn, T. Chavalit, A. Khamwut, N. P. T-Thienprasert, Biomed. Pharmacother., 2020, 130, 110552.
[37]	R. Baylon, J. Sun, L. Kovarik, M. Engelhard, H. Li, A.D. Winkelman, Y. Wang, Appl. Catal. B, 2018, 234, 337-346.
[38]	L. Silva-Calpa, P. C. Zonetti, C. P. Rodrigues, O. C. Alves, L. G. Appel, R. R. de Avillez, J. Mol. Catal. A, 2016, 425, 166-173.
[39]	H. Zhu, D. C. Rosenfeld, M. Harb, D. H. Anjum, M. N. Hedhili, S. Ould-Chikh, J. M. Basset, ACS Catal., 2016, 6, 2852-2866.
[40]	D. Salusso, E. Borfecchia, S. Bordiga, J. Phys. Chem. C, 2021, 125, 22249-22261.
[41]	J. E. Rorrer, F. D. Toste, A. T. Bell, ACS Catal., 2019, 9, 10588-10604.
[42]	M. Li, Z. Feng, G. Xiong, P. Ying, Q. Xin, C. Li, The J. Phys. Chem. B, 2001, 105, 8107-8111.
[43]	J. Das, S. K. Pradhan, D. R. Sahu, D. K. Mishra, S. N. Sarangi, B. B. Nayak, S. Verma, B. K. Roul, Physica B, 2010, 405, 2492-2497.
[44]	Z. Cheng, C. Jiang, X. Sun, G. Lan, X. Wang, L. He, Y. Li, H. Tang, Y. Li, Ind. Eng. Chem. Res., 2022, 61, 11699-11707.
[45]	Y. Xu, W. Yu, H. Zhang, J. Xin, X. He, B. Liu, F. Jiang, X. Liu, ACS Catal., 2021, 11, 13001-13019.
[46]	L. Pop, S. Rada, P. An, J. Zhang, M. Rada, R.C. Suciu, E. Culea, J. Synchrotron Radiat., 2020, 27, 970-978.
[47]	D. Y. Cho, H. S. Jung, C. S. Hwang, Phys. Rev. B, 2010, 82, 094104.
[48]	P. Ticali, D. Salusso, R. Ahmad, C. Ahoba-Sam, A. Ramirez, G. Shterk, K. A. Lomachenko, E. Borfecchia, S. Morandi, L. Cavallo, J. Gascon, S. Bordiga, U. Olsbye, Catal. Sci. Technol., 2021, 11, 1249-1268.
[49]	S. Han, D. Zhao, T. Otroshchenko, H. Lund, U. Bentrup, V. A. Kondratenko, N. Rockstroh, S. Bartling, D. E. Doronkin, J. D. Grunwaldt, U. Rodemerck, D. Linke, M. Gao, G. Jiang, E. V. Kondratenko, ACS Catal., 2020, 10, 8933-8949.
[50]	H. Chen, H. Cui, Y. Lv, P. Liu, F. Hao, W. Xiong, H. A Luo, Fuel, 2022, 314, 123035.
[51]	C. Zhou, J. Shi, W. Zhou, K. Cheng, Q. Zhang, J. Kang, Y. Wang, ACS Catal., 2020, 10, 302-310.
[52]	J. Sun, K. Zhu, F. Gao, C. Wang, J. Liu, C. Peden, Y. Wang, J. Am. Chem. Soc., 2011, 133, 11096-11099.
[53]	Z. Xie, H. Guo, E. Huang, Z. Mao, X. Chen, P. Liu, J. G. Chen, ACS Catal., 2022, 12, 8279-8290.
[54]	B. Yan, S. Yao, J. G. Chen, ChemCatChem, 2020, 12, 494-503.
[55]	S. A. Theofanidis, G. T. Kasun Kalhara Gunasooriya, I. Itskou, M. Tasioula, A. A. Lemonidou, ChemCatChem, 2022, 14, e202200032.
[56]	Y. Zhang, M. Chen, W. Wang, Y. Zhang, Catal. Sci. Technol., 2024, 14, 3924-3935.
[57]	X. Li, D. Kang, Z. He, J. Chen, F. Wang, Z. Zhang, Chem. Eng. J., 2024, 484, 149047.
[58]	X. Meng, F. Jin, A. Q. Peng, X. Jiang, X. Guo, G. Wu, Fuel, 2024, 363, 130968.
[59]	Y. Zheng, X. Zhang, J. Li, J. An, X. Zhu, X. Li, J. Catal., 2023, 428, 115130.
[60]	Y. Zheng, J. Li, X. Zhang, J. An, W. Xin, X. Zhu, X. Li, ACS Catal., 2023, 13, 11153-11163.
[61]	T. Lei, C. Miao, W. Hua, Y. Yue, Z. Gao, Catal. Lett., 2018, 148, 1634-1642.
[62]	M. Chen, H. Liu, Y. Wang, Z. Zhong, Y. Zeng, Y. Jin, D. Ye, L. Chen, J. Colloid Interface Sci., 2024, 660, 124-135.
[63]	T. Wan, F. Jin, X. Cheng, J. Gong, C. Wang, G. Wu, A. Liu, Appl. Catal. A, 2022, 637, 118542.
[64]	R. Koirala, R. Buechel, F. Krumeich, S. E. Pratsinis, A. Baiker, ACS Catal., 2015, 5, 690-702.
[65]	R. Koirala, R. Buechel, S. E. Pratsinis, A. Baiker, Appl. Catal. A, 2016, 527, 96-108.
[66]	I. I. Mishanin, T. V. Bogdan, A. E. Koklin, V. I. Bogdan, Chem. Eng. J., 2022, 446, 137184.
[67]	A. Peng, Y. Xing, G. Wu, X. Yu, X. Yi, X. Y. Liu, A. Zheng, F. Jin, Chem. Eng. J., 2024, 485, 150010.
[68]	S. Povari, S. Alam, S. Somannagari, L. Nakka, S. Chenna, Ind. Eng. Chem. Res., 2023, 62, 2573-2582.
[69]	Y. Zhang, Y. Zhao, T. Otroshchenko, H. Lund, M. M. Pohl, U. Rodemerck, D. Linke, H. Jiao, G. Jiang, E. V. Kondratenko, Nat. Commun., 2018, 9, 3794.
[70]	T. Otroshchenko, S. Sokolov, M. Stoyanova, V. A. Kondratenko, U. Rodemerck, D. Linke, E. V. Kondratenko, Angew. Chem. Int. Ed., 2015, 54, 15880-15883.
[71]	T. Otroshchenko, V. A. Kondratenko, U. Rodemerck, D. Linke, E. V. Kondratenko, J. Catal., 2017, 348, 282-290.
[72]	Y. Cheng, T. Lei, C. Miao, W. Hua, Y. Yue, Z. Gao, Microporous Mesoporous Mater., 2018, 268, 235-242.
[73]	M. Abdelgaid, J. Dean, G. Mpourmpakis, Catal. Sci. Technol., 2020, 10, 7194-7202.
[74]	H. Tian, J. Jiao, F. Zha, X. Guo, X. Tang, Y. Chang, H. Chen, Catal. Sci. Technol., 2022, 12, 799-811.
[75]	B. J. Hare, D. Maiti, Y. A. Daza, V. R. Bhethanabotla, J. N. Kuhn, ACS Catal., 2018, 8, 3021-3029.
[76]	Y. Yang, L. Wu, B. Yao, L. Zhang, M. Jung, Q. He, N. Yan, C. J. Liu, ACS Catal., 2024, 14, 13958-13972.
[77]	Z. Zhang, H. Tian, J. Sun, D. M. Meira, M. Zhang, X. Ding, D. Ji, C. Qiu, Z. Lu, L. Sun, Y. Zhang, W. Tu, Y. Zhou, X. Yang, J. Howe, L. Wang, S. Y. Tong, Z. Zou, Chem Catal., 2023, 3, 100644.
[78]	F. Gashoul Daresibi, A. A. Khodadadi, Y. Mortazavi, Appl. Catal. A, 2023, 655, 119117.
[79]	C. Liu, B. Qiao, T. Zhang, JACS Au, 2024, 4, 4129-4140.
[80]	G. Q. Yang, Y. J. He, Y. H. Song, J. Wang, Z. T. Liu, Z. W. Liu, Ind. Eng. Chem. Res., 2021, 60, 17850-17861.

Zn_xZrO催化剂上协同位点用于乙烷C-H键靶向性断裂及CO₂活化

Synergistic sites over the Zn_xZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO₂ activation

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