Citation: Bao-Lian ZHANG, Chang LIU, Su LIU, Hai-Bo ZHOU, Jun-Jie SU, Yang-Dong WANG, Dong-Sen MAO. ZnCr₂O₄/ZSM-5@Silicalite-1 to optimize the selectivity of one-step hydrogenation of CO₂ to aromatics[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(12): 2339-2348. doi: 10.11862/CJIC.2023.195 shu

ZnCr₂O₄/ZSM-5@Silicalite-1 to optimize the selectivity of one-step hydrogenation of CO₂ to aromatics

Bao-Lian ZHANG ^{1, 2} ,
Chang LIU ² ,
Su LIU ² ,
Hai-Bo ZHOU ² ,
Jun-Jie SU ² ,
Yang-Dong WANG ^2,, ,
Dong-Sen MAO ^1,,

1.
School of Chemical and Environment Engineering, Shanghai Institute of Technology, Shanghai 201418, China
2.
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Sinopec Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, China

Corresponding author: Yang-Dong WANG, wangyd.sshy@sinopec.com Dong-Sen MAO, dsmao@sit.edu.cn
Received Date: 13 April 2023
Revised Date: 2 November 2023

Figures(9)

The CO₂ hydrogenation reaction over the oxide-zeolite bifunctional catalyst yields a mixture of BTX (benzene, toluene, and xylene), C₉, and C₁₀₊ aromatic products, among which BTX is of the highest commercial value. To improve the distribution of the aromatic products and promote the production of BTX, the core-shell structured zeolite ZSM-5@Silicalite-1 was prepared by the epitaxial growth method in this work. According to the characterization results of powder X-ray diffraction (PXRD), N₂ adsorption-desorption, temperature-programmed desorption of NH₃ (NH₃-TPD), scanning electron microscope (SEM), transmission electron microscopy (TEM), and pyridine adsorption Fourier transform infrared spectroscopy (Py-IR), the inert Silicalite-1 shell is uniformly coated on the external surface of the ZSM-5 core, therefore changes its acidic properties especially reduces the external acidity, which contributes to improving the aromatic distribution. When applied in the one-step CO₂-to-aromatic reaction, the combination of ZSM-5@Silicalite-1 and Zn-Cr oxide resulted in a CO₂ conversion of 21.9% and aromatics selectivity of 79.3% under the conditions of V_H₂/V_CO₂=3.0, 1 200 mL·g^-1·h^-1, 320 ℃, and 4.0 MPa, and it gave a 33.5% of light aromatics in the overall aromatics, which was higher than 14.8% over the ZnCr₂O₄/ZSM-5 system. Additionally, in the one-step CO₂-to-aromatic reaction system, the by-products of CO and H₂O are generated from the side reaction of reverse water-gas shift (RWGS). Due to the higher hydrophobicity of Silicalite-1 than ZSM-5, H₂O is enriched at the interface between the oxide and core-shell zeolite, which can shift the reaction equilibrium of RWGS, thus inhibiting the generation of CO. As a result, the CO selectivity was significantly reduced at high space velocities compared with the unmodified oxide-zeolite system. At an optimal shell thickness, the ZnCr₂O₄/ZSM-5@Silicalite-1 bifunctional catalyst obtained a space-time yield of aromatics of 2.4 mmol·g^-1·h^-1 at 8 400 mL·g^-1·h^-1, which was 22% higher compared with ZnCr₂O₄/ZSM-5.
- carbon dioxide,
- aromatics,
- bifunctional catalysis,
- reaction path,
- core-shell zeolite
1. [1]
  Bushuyev O S, De L P, Dinh C T, Tao L, Saur G, Van D, Lagemaat J, Kelley S O, Sargent E H. What should we make with CO₂ and how can we make it[J]. Joule, 2018,2(5):825-832.
2. [2]
  Sutherland R B. Breaking compromises in CO₂ reduction[J]. Joule, 2017,1(4):643-645.
3. [3]
  Wang L, Mireille G, Wang H, Shao Y, Sun W, Athanasios A, Tountas , Thomas E, Wood , Li H, Loh J Y Y, Dong Y C, Xia M K, Li Y, Wang S H, Jia J, Qiu C Y, Qian C X, Kherani N P, He L, Zhang X H, Ozin G A. Photocatalytic hydrogenation of carbon dioxide with high selectivity to methanol at atmospheric pressure[J]. Joule, 2018,2(7):1369-1381.
4. [4]
  LI J L, LIANG Z H, LIANG D X, MA S L. Overview of development status of green hydrogen production and application technology under targets of carbon peak and carbon neutrality[J]. Distributed Energy, 2021,6(4):25-33.
5. [5]
  Li W H, Wang H Z, Jiang X, Zhu J, Liu Z M, Guo X W, Song C S. A short review of recent advances in CO₂ hydrogenation to hydrocarbons over heterogeneous catalysts[J]. RSC Adv., 2018,8(14):7651-7669.
6. [6]
  Zhang Z, Zheng Y, Qian L T, Luo D, Dou H Z, Wen G B, Yu A P, Chen Z W. Emerging trends in sustainable CO₂-management materials[J]. Adv. Mater., 2022,34(29)2201547.
7. [7]
  Yang X P, Song G Y, Li M Z, Chen C H, Wang Z H, Yuan H M, Zhang Z X, Liu D H. Selective production of aromatics directly from carbon dioxide hydrogenation over nNa-Cu-Fe₂O₃/HZSM-5[J]. Ind. Eng. Chem. Res., 2022,61(23):7787-7798.
8. [8]
  Wei J, Ge Q J, Yao R W, Wen Z Y, Fang C Y, Guo L S, Xu H Y, Sun J. Directly converting CO₂ into a gasoline fuel[J]. Nat. Commun., 2017,8(1)15174.
9. [9]
  Numpilai T, Cheng C K, Limtrakul J, Witoon T. Recent advances in light olefins production from catalytic hydrogenation of carbon dioxide[J]. Process Saf. Environ. Protect., 2021,151:401-427.
10. [10]
  Nezam I, Zhou W, Gusmao G S, Realff M J, Wang Y, Medford A J, Jones C W. Direct aromatization of CO₂ via combined CO₂ hydrogenation and zeolite-based acid catalysis[J]. J. CO₂ Util., 2021,45101405.
11. [11]
  Niziolek A M, Onel O, Floudas C A. Production of benzene, toluene, and xylenes from natural gas via methanol: Process synthesis and global optimization[J]. AIChE J., 2016,62(5):1531-1556.
12. [12]
  Wang D, Xie Z H, Porosoff M D, Chen J G. Recent advances in carbon dioxide hydrogenation to produce olefins and aromatics[J]. Chem, 2021,9:2277-2311.
13. [13]
  Larmier K, Liao W C, Tada S, Lam E, Verel R, Bansode A, Urakawa A, Comas-Vives A, Coperet C. CO₂-to-methanol hydrogenation on zirconia-supported copper nanoparticles: Reaction intermediates and the role of the metal-support interface[J]. Angew. Chem. Int. Ed., 2017,56(9):2318-2323.
14. [14]
  Wang J J, Li G, Li Z L, Tang C Z, Feng Z C, An H Y, Liu H L, Liu T F, Li C. A highly selective and stable ZnO-ZrO₂ solid solution catalyst for CO₂ hydrogenation to methanol[J]. Sci. Adv., 2017,3(10)e1701290.
15. [15]
  Shoinkhorova T, Cordero-Lanzac T, Ramirez A, Chung S, Dokania A, Ruiz-Martinez J, Gascon J. Highly selective and stable production of aromatics via high-pressure methanol conversion[J]. ACS Catal., 2021,11(6):3602-3613.
16. [16]
  Liu C, Su J J, Liu S, Zhou H B, Yuan X L, Ye Y C, Wang Y, Wang Y D, He H Y, Xie Z K. Insights into the key factor of zeolite morphology on the selective conversion of syngas to light aromatics over a Cr₂O₃/ZSM-5 catalyst[J]. ACS Catal., 2020,10(24):15227-15237.
17. [17]
  Liu C, Liu S, Zhou H B, Su J J, Jiao W Q, Zhang L, Wang Y D, He H Y, Xie Z K. Selective conversion of syngas to aromatics over metal oxide/HZSM‑5 catalyst by matching the activity between CO hydrogenation and aromatization[J]. Appl. Catal. A-Gen., 2019,585117206.
18. [18]
  Cui X, Gao P, Li S G, Yang C G, Liu Z, Wang H, Zhong L S, Sun Y H. Selective production of aromatics directly from carbon dioxide hydrogenation[J]. ACS Catal., 2019,9(5):3866-3876.
19. [19]
  Yang W, Gao W Z, Kazumi S, Li H J, Yang G H, Tsubaki N. Direct and oriented conversion of CO₂ to value-added aromatics[J]. Chem. -Eur. J., 2019,25(20):5149-5153.
20. [20]
  Wang Y, Tan L, Tan M H, Zhang P P, Fang Y, Yoneyama Y, Yang G H, Tsubaki N. Rationally designing bifunctional catalysts as an efficient strategy to boost CO₂ hydrogenation producing value-added aromatics[J]. ACS Catal., 2018,9(2):895-901.
21. [21]
  Liu C, Su J J, Xiao Yu, Zhou J, Liu S, Zhou H B, Wang Y D, Wang C M, Zheng X S, Xie Z K. Constructing directional component distribution in a bifunctional catalyst to boost the tandem reaction of syngas conversion[J]. Chem Catal., 2021,1(4):896-907.
22. [22]
  REN K, ZHANG L L, LI Z, FU T J. Structure-activity relationship and reaction characteristics of propene aromatization catalyzed by ZSM-5[J]. Chinese J. Inorg. Chem., 2022,38(6):1090-1102. doi: 10.11862/CJIC.2022.115
23. [23]
  Brus J, Kobera L, Schoefberger W, Urbanová M, Klein P, Sazama P, Sklenak S, Fishchuk A, Dědeek J. Structure of framework aluminum Lewis sites and perturbed aluminum atoms in zeolites as determined by ²⁷Al{¹H} REDOR (3Q) MAS NMR spectroscopy and DFT/molecular mechanics[J]. Angew. Chem. Int. Ed., 2015,54(2):541-545.
24. [24]
  Corma A, Fornés V, Forni L, Márquez F, Márquez F, Martınez-Triguero J, Moscotti D. 2, 6-Di-tert-butyl-pyridine as a probe molecule to measure external acidity of zeolites[J]. J. Catal., 1998,179(2):451-458.
25. [25]
  Cheng K, Zhou Z, Kang J C, He S, Shi S L, Zhang Q H, Pan Y, Wen W, Wang Y. Bifunctional catalysts for one-step conversion of syngas into aromatics with excellent selectivity and stability[J]. Chem, 2017,3(2):334-347.
26. [26]
  Huang Z, Wang S, Qin F, Huang L, Yue Y H, Hua W M, Qiao M H, He H Y, Shen W, Xu H L. Ceria-zirconia/zeolite bifunctional catalyst for highly selective conversion of syngas into aromatics[J]. ChemCatChem, 2018,10(20):4519-4524.
27. [27]
  Zhang P P, Tan L, Yang G H, Tsubaki N. One-pass selective conversion of syngas to para-xylene[J]. Chem. Sci., 2017,8(12):7941-7946.
1. [1]
  Xiaofei Liu , He Wang , Li Tao , Weimin Ren , Xiaobing Lu , Wenzhen Zhang . Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide. Acta Physico-Chimica Sinica, 2024, 40(9): 2307008-0. doi: 10.3866/PKU.WHXB202307008
2. [2]
  Yanhui Guo , Li Wei , Zhonglin Wen , Chaorong Qi , Huanfeng Jiang . Recent Progress on Conversion of Carbon Dioxide into Carbamates. Acta Physico-Chimica Sinica, 2024, 40(4): 2307004-0. doi: 10.3866/PKU.WHXB202307004
3. [3]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Research on Cu-Based and Pt-Based Catalysts for Hydrogen Production through Methanol Steam Reforming. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-0. doi: 10.1016/j.actphy.2025.100049
4. [4]
  Honghong Zhang , Zhen Wei , Derek Hao , Lin Jing , Yuxi Liu , Hongxing Dai , Weiqin Wei , Jiguang Deng . 非均相催化CO₂与烃类协同催化转化的最新进展. Acta Physico-Chimica Sinica, 2025, 41(7): 100073-0. doi: 10.1016/j.actphy.2025.100073
5. [5]
  Yan Kong , Wei Wei , Lekai Xu , Chen Chen . Electrochemical Synthesis of Organonitrogen Compounds from N-integrated CO₂ Reduction Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2307049-0. doi: 10.3866/PKU.WHXB202307049
6. [6]
  Hui-Ying Chen , Hao-Lin Zhu , Pei-Qin Liao , Xiao-Ming Chen . Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306046-0. doi: 10.3866/PKU.WHXB202306046
7. [7]
  Qiang Zhang , Yuanbiao Huang , Rong Cao . Imidazolium-Based Materials for CO₂ Electroreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306040-0. doi: 10.3866/PKU.WHXB202306040
8. [8]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029
9. [9]
  Zixuan Zhao , Miao Fan . “Carbon” with No “Ester”: A Boundless Journey of CO₂ Transformation. University Chemistry, 2025, 40(7): 213-217. doi: 10.12461/PKU.DXHX202409040
10. [10]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
11. [11]
  Yueguang Chen , Wenqiang Sun . “Carbon” Adventures. University Chemistry, 2024, 39(9): 248-253. doi: 10.3866/PKU.DXHX202308074
12. [12]
  Jianan Hong , Chenyu Xu , Yan Liu , Changqi Li , Menglin Wang , Yanwei Zhang . Decoding the interfacial competition between hydrogen evolution and CO₂ reduction via edge-active-site modulation in photothermal catalysis. Acta Physico-Chimica Sinica, 2025, 41(9): 100099-0. doi: 10.1016/j.actphy.2025.100099
13. [13]
  Bizhu Shao , Huijun Dong , Yunnan Gong , Jianhua Mei , Fengshi Cai , Jinbiao Liu , Dichang Zhong , Tongbu Lu . Metal-Organic Framework-Derived Nickel Nanoparticles for Efficient CO₂ Electroreduction in Wide Potential Windows. Acta Physico-Chimica Sinica, 2024, 40(4): 2305026-0. doi: 10.3866/PKU.WHXB202305026
14. [14]
  Haoran Zhang , Yaxin Jin , Peng Kang , Sheng Zhang . The Convergence and Innovative Application of Artificial Intelligence in Scientific Research: A Case Study of Electrocatalytic Carbon Dioxide Reduction in the Context of the Dual-Carbon Strategy. University Chemistry, 2025, 40(9): 148-155. doi: 10.12461/PKU.DXHX202412099
15. [15]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 2406012-0. doi: 10.3866/PKU.WHXB202406012
16. [16]
  Xudong Lv , Tao Shao , Junyan Liu , Meng Ye , Shengwei Liu . Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals. Acta Physico-Chimica Sinica, 2024, 40(5): 2305028-0. doi: 10.3866/PKU.WHXB202305028
17. [17]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
18. [18]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
19. [19]
  Hailang JIA , Pengcheng JI , Hongcheng LI . Preparation and performance of nickel doped ruthenium dioxide electrocatalyst for oxygen evolution. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1632-1640. doi: 10.11862/CJIC.20240398
20. [20]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(1760)
HTML views(467)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

ZnCr2O4/ZSM-5@Silicalite-1 to optimize the selectivity of one-step hydrogenation of CO2 to aromatics

Metrics

通讯作者: 陈斌, bchen63@163.com

ZnCr₂O₄/ZSM-5@Silicalite-1 to optimize the selectivity of one-step hydrogenation of CO₂ to aromatics