Abstract
Metal oxide-promoted Rh-based catalysts have been widely used for CO2 hydrogenation, especially for the ethanol synthesis. However, this reaction usually suffers low CO2 conversion and alcohols selectivity due to the formation of byproducts methane and CO. This paper describes an efficient vanadium oxide promoted Rh-based catalysts confined in mesopore MCM-41. The Rh-0.3VOx/MCM-41 catalyst shows superior conversion (~12%) and ethanol selectivity (~24%) for CO2 hydrogenation. The promoting effect can be attributed to the synergism of high Rh dispersion by the confinement effect of MCM-41 and the formation of VOx-Rh interface sites. Experimental and theoretical results indicate the formation of til-CO at VOx-Rh interface sites is easily dissociated into *CHx, and then *CHx can be inserted by CO to form CH3CO*, followed by CH3CO* hydrogenation to ethanol.
Similar content being viewed by others
References
Wang W, Wang S, Ma X, Gong J. Chem Soc Rev, 2011, 40: 3703
Porosoff MD, Yan B, Chen JG. Energy Environ Sci, 2016, 9: 62–73
Yang H, Zhang C, Gao P, Wang H, Li X, Zhong L, Wei W, Sun Y. Catal Sci Technol, 2017, 7: 4580–4598
Aresta M, Dibenedetto A, Angelini A. Chem Rev, 2014, 114: 1709–1742
Devarapalli M, Atiyeh HK. Biofuel Res J, 2015, 2: 268–280
Luk HT, Mondelli C, Ferré DC, Stewart JA, Pérez-Ramírez J. Chem Soc Rev, 2017, 46: 1358–1426
Wang L, Wang L, Zhang J, Liu X, Wang H, Zhang W, Yang Q, Ma J, Dong X, Yoo SJ, Kim JG, Meng X, Xiao FS. Angew Chem Int Ed, 2018, 57: 6104–6108
He Z, Qian Q, Ma J, Meng Q, Zhou H, Song J, Liu Z, Han B. Angew Chem Int Ed, 2016, 55: 737–741
Inui T, Yamamoto T, Inoue M, Hara H, Takeguchi T, Kim JB. Appl Catal A-Gen, 1999, 186: 395–406
Takagawa M, Okamoto A, Fujimura H, Izawa Y, Arakawa H. Stud Surf Sci Catal, 1998, 114: 525–528
Higuchi K, Haneda Y, Tabata K, Nakahara Y, Takagawa M. Stud Surf Sci Catal, 1998, 114: 517–520
Li S, Guo H, Luo C, Zhang H, Xiong L, Chen X, Ma L. Catal Lett, 2013, 143: 345–355
Kusama H, Okabe K, Sayama K, Arakawa H. Appl Organometal Chem, 2000, 14: 836–840
Kitamura Bando K, Soga K, Kunimori K, Arakawa H. Appl Catal A-Gen, 1998, 175: 67–81
Kusama H, Okabe K, Sayama K, Arakawa H. Energy, 1997, 22: 343–348
Kusama H, Okabe K, Sayama K, Arakawa H. Catal Today, 1996, 28: 261–266
Kusama H, Bando KK, Okabe K, Arakawa H. Appl Catal A-Gen, 2001, 205: 285–294
Kusama H, Okabe K, Arakawa H. Appl Catal A-Gen, 2001, 207: 85–94
Yang C, Mu R, Wang G, Song J, Tian H, Zhao ZJ, Gong J. Chem Sci, 2019, 10: 3161–3167
Carrillo P, Shi R, Teeluck K, Senanayake SD, White MG. ACS Catal, 2018, 8: 7279–7286
Palomino RM, Magee JW, Llorca J, Senanayake SD, White MG. J Catal, 2015, 329: 87–94
Wang Y, Luo H, Liang D, Bao X. J Catal, 2000, 196: 46–55
Yang N, Yoo JS, Schumann J, Bothra P, Singh JA, Valle E, Abild-Pedersen F, Nørskov JK, Bent SF. ACS Catal, 2017, 7: 5746–5757
Prieto G, Concepción P, Martínez A, Mendoza E. J Catal, 2011, 280: 274–288
Chen Y, Zhang H, Ma H, Qian W, Jin F, Ying W. Catal Lett, 2018, 148: 691–698
Schwartz V, Campos A, Egbebi A, Spivey JJ, Overbury SH. ACS Catal, 2011, 1: 1298–1306
Mo X, Gao J, Umnajkaseam N, Goodwin Jr. JG. J Catal, 2009, 267: 167–176
Matsubu JC, Yang VN, Christopher P. J Am Chem Soc, 2015, 137: 3076–3084
Arakawa H, Takeuchi K, Matsuzaki T, Sugi Y. Chem Lett, 1984, 13: 1607–1610
Kresse G, Hafner J. Phys Rev B, 1993, 47: 558–561
Kresse G, Furthmüller J. Phys Rev B, 1996, 54: 11169–11186
Perdew JP, Burke K, Ernzerhof M. Phys Rev Lett, 1996, 77: 3865–3868
Blöchl PE. Phys Rev B, 1994, 50: 17953–17979
Henkelman G, Uberuaga BP, Jónsson H. J Chem Phys, 2000, 113: 9901–9904
Wu Z, Kim HS, Stair PC, Rugmini S, Jackson SD. J Phys Chem B, 2005, 109: 2793–2800
Liu G, Zhao ZJ, Wu T, Zeng L, Gong J. ACS Catal, 2016, 6: 5207–5214
Pan X, Fan Z, Chen W, Ding Y, Luo H, Bao X. Nat Mater, 2007, 6: 507–511
Bulánek R, Čičmanec P, Setnička M. Phys Procedia, 2013, 44: 195–205
Kip BJ, Smeets PAT, van Grondelle J, Prins R. Appl Catal, 1987, 33: 181–208
Beutel T, Siborov V, Tesche B, Knözinger H. J Catal, 1997, 167: 379–390
Yamagishi T, Furikado I, Ito S, Miyao T, Naito S, Tomishige K, Kunimori K. J Mol Catal A-Chem, 2006, 244: 201–212
Liu Y, Göeltl F, Ro I, Ball MR, Sener C, Aragão IB, Zanchet D, Huber GW, Mavrikakis M, Dumesic JA. ACS Catal, 2017, 7: 4550–4563
Zhang W, Wang L, Liu H, Hao Y, Li H, Khan MU, Zeng J. Nano Lett, 2017, 17: 788–793
Swapnesh A, Srivastava VC, Mall ID. Chem Eng Technol, 2014, 37: 1765–1777
He X. Int J Oil Gas Coal Eng, 2017, 5: 145–152
Heyl D, Rodemerck U, Bentrup U. ACS Catal, 2016, 6: 6275–6284
Matsubu JC, Zhang S, DeRita L, Marinkovic NS, Chen JG, Graham GW, Pan X, Christopher P. Nat Chem, 2017, 9: 120–127
Stevenson SA, Lisitsyn A, Knoezinger H. J Phys Chem, 1990, 94: 1576–1581
Wang Y, Song Z, Ma D, Luo H, Liang D, Bao X. J Mol Catal A-Chem, 1999, 149: 51–61
Wang J, Li G, Li Z, Tang C, Feng Z, An H, Liu H, Liu T, Li C. Sci Adv, 2017, 3: e1701290
Graciani J, Mudiyanselage K, Xu F, Baber AE, Evans J, Senanayake SD, Stacchiola DJ, Liu P, Hrbek J, Fernández Sanz J, Rodriguez JA. Science, 2014, 345: 546–550
Wang X, Hong Y, Shi H, Szanyi J. J Catal, 2016, 343: 185–195
Chen Y, Choi S, Thompson LT. J Catal, 2016, 343: 147–156
Schweicher J, Bundhoo A, Kruse N. J Am Chem Soc, 2012, 134: 16135–16138
Zhao YH, Sun K, Ma X, Liu J, Sun D, Su HY, Li WX. Angew Chem Int Ed, 2011, 50: 5335–5338
Kusama H, Bando KK, Okabe K, Arakawa H. Appl Catal A-Gen, 2000, 197: 255–268
Sun J, Cai Q, Wan Y, Wan S, Wang L, Lin J, Mei D, Wang Y. ACS Catal, 2016, 6: 5771–5785
Kattel S, Yu W, Yang X, Yan B, Huang Y, Wan W, Liu P, Chen JG. Angew Chem Int Ed, 2016, 55: 7968–7973
Kattel S, Liu P, Chen JG. J Am Chem Soc, 2017, 139: 9739–9754
Acknowledgements
This work was supported by the National Key R&D Program of China (2016YFB0600901), the National Natural Science Foundation of China (21525626, 21603159, 21676181), and the Program of Introducing Talents of Discipline to Universities (B06006).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Conflict of interest
The authors declare that they have no conflict of interest.
Supporting Information
Rights and permissions
About this article
Cite this article
Wang, G., Luo, R., Yang, C. et al. Active sites in CO2 hydrogenation over confined VOx-Rh catalysts. Sci. China Chem. 62, 1710–1719 (2019). https://doi.org/10.1007/s11426-019-9590-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-019-9590-6