Citation: YIN Yazhi, HU Bing, LIU Guoliang, ZHOU Xiaohai, HONG Xinlin. ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol[J]. Acta Physico-Chimica Sinica, ;2019, 35(3): 327-336. doi: 10.3866/PKU.WHXB201803212 shu

ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China

Corresponding author: ZHOU Xiaohai, zxh7954@hotmail.com HONG Xinlin, hongxl@whu.edu.cn
Received Date: 26 February 2018
Revised Date: 12 March 2018
Accepted Date: 19 March 2018
Available Online: 21 March 2018
Fund Project: the National Science Foundation of China 21373153The project was supported by the National Science Foundation of China (21373153)

Catalytic CO₂ hydrogenation to methanol is a promising route to mitigate the negative effects of anthropogenic CO₂. To develop an efficient Pd/ZnO catalyst, increasing the contact between Pd and ZnO is of the utmost importance, because "naked" Pd favors CO production via the reverse water-gas shift path. Here, we have utilized a ZnO@ZIF-8 core-shell structure to synthesize Pd/ZnO catalysts via Pd immobilization and calcination. The merit of this method is that the porous outer layer can offer abundant "guest rooms" for Pd, ensuring intimate contact between Pd and the post-generated ZnO. The synthesized Pd/ZnO catalysts (PZZ8-T, T denotes the temperature of calcination in degree Celsius) is compared with a ZnO nanorod-immobilized Pd catalyst (PZ). When the catalytic reaction was performed at lower reaction temperatures (250, 270, and 290 ℃), the highest methanol space time yield (STY) and highest STY per Pd achieved by PZ at 290 ℃ were 0.465 g g_cat^-1 h^-1 and 13.0 g g_Pd^-1 h^-1, respectively. However, all the PZZ8-T catalysts exhibited methanol selectivity values greater than 67.0% at 290 ℃, in sharp contrast to a methanol selectivity value of 32.8% for PZ at the same temperature. Thus, we performed additional investigations of the PZZ8-T catalysts at 310 and 360 ℃, which are unusually high temperatures for CO₂ hydrogenation to methanol because the required endothermic reaction is expected to be severely inhibited at such high temperatures. Interestingly, the PZZ8-T catalysts were observed to achieve a methanol selectivity value of approximately 60% at 310 ℃, and PZZ8-400 was observed to maintain a methanol selectivity value of 51.9% even at a temperature of 360 ℃. Thus, PZZ8-400 attains the highest methanol STY of 0.571 g g_cat^-1 h^-1at 310 ℃. For a better understanding of the structure-performance relationship, we characterized the catalysts using different techniques, focusing especially on the surface properties. X-ray photoelectron spectroscopy (XPS) results indicated a linear relationship between the methanol selectivity and the surface PdZn : Pd ratio, proving that the surface PdZn phase is the active site for CO₂ hydrogenation to methanol. Furthermore, analysis of the XPS O 1s spectrum together with the electronic paramagnetic resonance results revealed that both, the oxygen vacancy as well as the ZnO polar surface, played important roles in CO₂ activation. Chemisorption techniques provided further quantitative and qualitative information regarding the Pd-ZnO interface that is closely related to the CO₂ conversion rate. We believe that our results can provide insight into the catalytic reaction of CO₂ hydrogenation from the perspective of surface science. In addition, this work is an illustrative example of the use of novel chemical structures in the fabrication of superior catalysts using a traditional formula.
- ZnO@ZIF-8,
- PdZn alloy,
- Methanol synthesis,
- CO₂ hydrogenation,
- Surface oxygen vacancy
1. [1]
  Li, Y.; Chan, S. H.; Sun, Q. Nanoscale 2015, 7, 8663. doi: 10.1039/C5NR00092K doi: 10.1039/C5NR00092K
2. [2]
  Porosoff, M. D.; Yan, B.; Chen, J. G. Energy Environ. Sci. 2016, 9, 62. doi: 10.1039/C5EE02657A doi: 10.1039/C5EE02657A
3. [3]
  Lee, S. Methanol Synthesis Technology; Taylor & Francis: Arbingdon, UK, 1989.
4. [4]
  Stiles, A. AIChE J. 1977, 23, 362. doi: 10.1002/aic.690230321 doi: 10.1002/aic.690230321
5. [5]
  Behrens, M.; Studt, F.; Kasatkin, I.; Kühl, S.; Hävecker, M.; Abild-Pedersen, F.; Zander, S.; Girgsdies, F.; Kurr, P.; Kniep, B. L.; et al. Science 2012, 336, 893. doi: 10.1126/science.1219831 doi: 10.1126/science.1219831
6. [6]
  Kattel, S.; Ramirez, P. J.; Chen, J. G.; Rodriguez, J. A.; Liu, P. Science 2017, 355, 1296. doi: 10.1126/science.aal3573 doi: 10.1126/science.aal3573
7. [7]
  Erdöhelyi, A.; Pásztor, M.; Solymosi, F. J. Catal. 1986, 98, 166. doi: 10.1016/0021-9517(86)90306-4 doi: 10.1016/0021-9517(86)90306-4
8. [8]
  Jadhav, S. G.; Vaidya, P. D.; Bhanage, B. M.; Joshi, J. B. Chem. Eng. Res. Des. 2014, 92, 2557. doi: 10.1016/j.cherd.2014.03.005 doi: 10.1016/j.cherd.2014.03.005
9. [9]
  Liang, X. -L.; Dong, X.; Lin, G. -D.; Zhang, H. -B. Appl. Catal. B-Environ. 2009, 88, 315. doi: 10.1016/j.apcatb.2008.11.018 doi: 10.1016/j.apcatb.2008.11.018
10. [10]
  Xu, J.; Su, X.; Liu, X.; Pan, X.; Pei, G.; Huang, Y.; Wang, X.; Zhang, T.; Geng, H. Appl. Catal. A: Gen. 2016, 514, 51. doi: 10.1016/j.apcata.2016.01.006 doi: 10.1016/j.apcata.2016.01.006
11. [11]
  Liao, F.; Wu, X. -P.; Zheng, J.; Li, M. M. -J.; Kroner, A.; Zeng, Z.; Hong, X.; Yuan, Y.; Gong, X. -Q.; Tsang, S. C. E. Green Chem. 2017, 19, 270. doi: 10.1039/C6GC02366E doi: 10.1039/C6GC02366E
12. [12]
  Mueller, M.; Hermes, S.; Kaehler, K.; van den Berg, M. W. E.; Muhler, M.; Fischer, R. A. Chem. Mater. 2008, 20, 4576. doi: 10.1021/cm703339h doi: 10.1021/cm703339h
13. [13]
  An, B.; Zhang, J.; Cheng, K.; Ji, P.; Wang, C.; Lin, W. J. Am. Chem. Soc. 2017, 139, 3834. doi: 10.1021/jacs.7b00058 doi: 10.1021/jacs.7b00058
14. [14]
  Wang, Y. Acta Phs. -Chim. Sin. 2017, 33, 857. doi: 10.3866/PKU.WHXB201703172
15. [15]
  Pan, Y.; Liu, Y.; Zeng, G.; Zhao, L.; Lai, Z. Chem. Comm. 2011, 47, 2071. doi: 10.1039/C0CC05002D doi: 10.1039/C0CC05002D
16. [16]
  Jiang, H. -L.; Liu, B.; Lan, Y. -Q.; Kuratani, K.; Akita, T.; Shioyama, H.; Zong, F.; Xu, Q. J. Am. Chem. Soc. 2011, 133, 11854. doi: 10.1021/ja203184k doi: 10.1021/ja203184k
17. [17]
  Ding, S.; Yan, Q.; Jiang, H.; Zhong, Z.; Chen, R.; Xing, W. Chem. Eng. J. 2016, 296, 146. doi: 10.1016/j.cej.2016.03.098 doi: 10.1016/j.cej.2016.03.098
18. [18]
  Koo, W. -T.; Choi, S. -J.; Kim, S. -J.; Jang, J. -S.; Tuller, H. L.; Kim, I. -D. J. Am. Chem. Soc. 2016, 138, 13431. doi: 10.1021/jacs.6b09167 doi: 10.1021/jacs.6b09167
19. [19]
  Li, F. -L.; Li, H. -X.; Lang, J. -P. CrystEngComm 2016, 18, 1760. doi: 10.1039/C5CE02219C doi: 10.1039/C5CE02219C
20. [20]
  Wang, X.; Liu, J.; Leong, S.; Lin, X.; Wei, J.; Kong, B.; Xu, Y.; Low, Z.- X.; Yao, J.; Wang, H. ACS Appl. Mater. Inter. 2016, 8, 9080. doi: 10.1021/acsami.6b00028 doi: 10.1021/acsami.6b00028
21. [21]
  Zhan, W. -W.; Kuang, Q.; Zhou, J. -Z.; Kong, X. -J.; Xie, Z. -X.; Zheng, L. -S. J. Am. Chem. Soc. 2013, 135, 1926. doi: 10.1021/ja311085e doi: 10.1021/ja311085e
22. [22]
  Liu, B.; Zeng, H. C. Langmuir 2004, 20, 4196. doi: 10.1021/la035264o doi: 10.1021/la035264o
23. [23]
  XRD data bank attached to X'Pert PRO X-ray Diffractometer; PANalytical: The Netherlands, 2003; PDF#43-1024 and PDF#46-1043.
24. [24]
  Lu, H. S.; Zhang, H.; Liu, R.; Zhang, X.; Zhao, H.; Wang, G. Appl. Surf. Sci. 2017, 392, 402. doi: 10.1016/j.apsusc.2016.09.045 doi: 10.1016/j.apsusc.2016.09.045
25. [25]
  Tian, H.; Fan, H.; Li, M.; Ma, L. ACS Sens. 2016, 1, 243. doi: 10.1021/acssensors.5b00236 doi: 10.1021/acssensors.5b00236
26. [26]
  Jing, Z.; Zhan, J. Adv. Mater. 2008, 20, 4547. doi: 10.1002/adma.200800243 doi: 10.1002/adma.200800243
27. [27]
  Hu, H. F.; He, T. Acta Phys. -Chim. Sin. 2016, 32, 543. doi: 10.3866/PKU.WHXB201511194
28. [28]
  Hariharan, C. Appl. Catal. A: Gen. 2006, 304, 55. doi: 10.1016/j.apcata.2006.02.020 doi: 10.1016/j.apcata.2006.02.020
29. [29]
  Hwang, Y. K.; Hong, D. Y.; Chang, J. S.; Jhung, S. H.; Seo, Y. K.; Kim, J.; Vimont, A.; Daturi, M.; Serre, C.; Férey, G. Angew. Chem. Int. Ed. 2008, 47, 4144. doi: 10.1002/anie.200705998 doi: 10.1002/anie.200705998
30. [30]
  Jun, L.; Zhu, Q. -L.; Xu, Q. Chem. Commun. 2014, 50, 5899. doi: 10.1039/C4CC00785A doi: 10.1039/C4CC00785A
31. [31]
  Graaf, G. H.; Sijtsema, P.; Stamhuis, E. J.; Joosten, G. E. H. Chem. Eng. Sci. 1986, 41, 2883. doi: 10.1016/0009-2509(86)80019-7 doi: 10.1016/0009-2509(86)80019-7
32. [32]
  Djurisic, A. B.; Choy, W. C. H.; Roy, V. A. L.; Leung, Y. H.; Kwong, C. Y.; Cheah, K. W.; Rao, T. K. G.; Chan, W. K.; Lui, H. T.; Surya, C. Adv. Funct. Mater. 2004, 14, 856. doi: 10.1002/adfm.200305082 doi: 10.1002/adfm.200305082
33. [33]
  Ischenko, V.; Polarz, S.; Grote, D.; Stavarache, V.; Fink, K.; Driess, M. Adv. Funct. Mater. 2005, 15, 1945. doi: 10.1002/adfm.200500087 doi: 10.1002/adfm.200500087
34. [34]
  Rodriguez, J. A. J. Phys. Chem. 1994, 98 (22), 5758. doi: 10.1021/j100073a031 doi: 10.1021/j100073a031
35. [35]
  Chen, M.; Wang, X.; Yu, Y. H.; Pei, Z. L.; Bai, X. D.; Sun, C.; Huang, R. F.; Wen, L. S. Appl. Surf. Sci. 2000, 158, 134. doi: 10.1016/S0169-4332(99)00601-7 doi: 10.1016/S0169-4332(99)00601-7
36. [36]
  Wei, X. Q.; Man, B. Y.; Liu, M.; Xue, C. S.; Zhuang, H. Z.; Yang, C. Phys. B: Condens. Matter 2007, 388, 145. doi: 10.1016/j.physb.2006.05.346 doi: 10.1016/j.physb.2006.05.346
37. [37]
  Behrens, M.; Zander, S.; Kurr, P.; Jacobsen, N.; Senker, J.; Koch, G.; Ressler, T.; Fischer, R. W.; Schlögl, R. J. Am. Chem. Soc. 2013, 135, 6061. doi: 10.1021/ja310456f doi: 10.1021/ja310456f
38. [38]
  Liao, F.; Huang, Y.; Ge, J.; Zheng, W.; Tedsree, K.; Collier, P.; Hong, X.; Tsang, S. C. Angew. Chem. Int. Ed. 2011, 50, 2162. doi: 10.1002/anie.201007108 doi: 10.1002/anie.201007108
39. [39]
  Ehrlich, D.; Wohlrab, S.; Wambach, J.; Kuhlenbeck, H.; Freund, H. J. Vacuum 1990, 41, 157. doi: 10.1016/S0042-207X(05)80144-7 doi: 10.1016/S0042-207X(05)80144-7
1. [1]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
2. [2]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
3. [3]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
4. [4]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . 软模板法诱导Cu/Al₂O₃深孔道结构促进等离子催化CO₂加氢制二甲醚. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
5. [5]
  Guang-Xu Duan , Queting Chen , Rui-Rui Shao , Hui-Huang Sun , Tong Yuan , Dong-Hao Zhang . Encapsulating lipase on the surface of magnetic ZIF-8 nanosphers with mesoporous SiO₂ nano-membrane for enhancing catalytic performance. Chinese Chemical Letters, 2025, 36(2): 109751-. doi: 10.1016/j.cclet.2024.109751
6. [6]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
7. [7]
  Zhaojun Liu , Zerui Mu , Chuanbo Gao . Alloy nanocrystals: Synthesis paradigms and implications. Chinese Journal of Structural Chemistry, 2023, 42(11): 100156-100156. doi: 10.1016/j.cjsc.2023.100156
8. [8]
  Tianbo Jia , Lili Wang , Zhouhao Zhu , Baikang Zhu , Yingtang Zhou , Guoxing Zhu , Mingshan Zhu , Hengcong Tao . Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products. Chinese Chemical Letters, 2024, 35(5): 108692-. doi: 10.1016/j.cclet.2023.108692
9. [9]
  Qiyan Wu , Qing Li . Topologically close-packed intermetallic alloy electrocatalysts for CO₂ reduction towards high value-added multi-carbon chemicals. Chinese Chemical Letters, 2025, 36(1): 110384-. doi: 10.1016/j.cclet.2024.110384
10. [10]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
11. [11]
  Bing Shen , Tongwei Yuan , Wenshuang Zhang , Yang Chen , Jiaqiang Xu . Complex shell Fe-ZnO derived from ZIF-8 as high-quality acetone MEMS sensor. Chinese Chemical Letters, 2024, 35(11): 109490-. doi: 10.1016/j.cclet.2024.109490
12. [12]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255
13. [13]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
14. [14]
  Jiaqi Ma , Lan Li , Yiming Zhang , Jinjie Qian , Xusheng Wang . Covalent organic frameworks: Synthesis, structures, characterizations and progress of photocatalytic reduction of CO2. Chinese Journal of Structural Chemistry, 2024, 43(12): 100466-100466. doi: 10.1016/j.cjsc.2024.100466
15. [15]
  Zhen Zhang , Xue-ling Chen , Xiu-Mei Xie , Tian-Yu Gao , Jing Qin , Jun-Jie Li , Chao Feng , Da-Gang Yu . Iron-promoted carbonylation–rearrangement of α-aminoaryl-tethered alkylidenecyclopropanes with CO₂: Facile synthesis of quinolinofurans. Chinese Chemical Letters, 2025, 36(4): 110056-. doi: 10.1016/j.cclet.2024.110056
16. [16]
  Ming Huang , Xiuju Cai , Yan Liu , Zhuofeng Ke . Base-controlled NHC-Ru-catalyzed transfer hydrogenation and α-methylation/transfer hydrogenation of ketones using methanol. Chinese Chemical Letters, 2024, 35(7): 109323-. doi: 10.1016/j.cclet.2023.109323
17. [17]
  Kaili Wang , Pengcheng Liu , Mingzhe Wang , Tianran Wei , Jitao Lu , Xingling Zhao , Zaiyong Jiang , Zhimin Yuan , Xijun Liu , Jia He . Modulating d-d orbitals coupling in PtPdCu medium-entropy alloy aerogels to boost pH-general methanol electrooxidation performance. Chinese Chemical Letters, 2025, 36(4): 110532-. doi: 10.1016/j.cclet.2024.110532
18. [18]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
19. [19]
  Xiuzheng Deng , Yi Ke , Jiawen Ding , Yingtang Zhou , Hui Huang , Qian Liang , Zhenhui Kang . Construction of ZnO@CDs@Co₃O₄ sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO₂ reduction. Chinese Chemical Letters, 2024, 35(4): 109064-. doi: 10.1016/j.cclet.2023.109064
20. [20]
  Lu Dai , Yuxin Ren , Shuang Li , Meidi Wang , Chentao Hu , Ya-Pan Wu , Guangtong Hai , Dong-Sheng Li . Room-temperature synthesis of Co(OH)₂/Mo₂TiC₂T_x hetero-nanosheets with interfacial coupling for enhanced oxygen evolution reaction. Chinese Chemical Letters, 2025, 36(4): 109774-. doi: 10.1016/j.cclet.2024.109774

Get Citation

PDF

XML

Metrics

PDF Downloads(21)
Abstract views(544)
HTML views(49)

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

ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO2 to Methanol

Metrics

通讯作者: 陈斌, bchen63@163.com

ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol