Citation: Dan LUO, Xingcheng LIU, Dong LI, Tong CHANG. Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(11): 2337-2344. doi: 10.11862/CJIC.20250003 shu

Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts

Dan LUO ¹ ,
Xingcheng LIU ^{2, 3} ,
Dong LI ¹ ,
Tong CHANG ^1,,

1.
Shanxi Key Laboratory of Ecological Protection and Resources Utilization of Yuncheng Salt Lake, Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Tong CHANG, luodan@ycu.edu.cn
Received Date: 17 February 2025
Revised Date: 18 September 2025

Figures(8)

Employing the first-principles density functional theory (DFT), an in-depth investigation was conducted into the structure, electronic properties, and CO activity of hydroxylated SiO₂(001) surface-supported Co_n (where n is the number of cobalt atoms, n=1-6) materials [Co_n/SiO₂(001)]. Here, n=1 represents a single Co atom, while n=2-6 denotes Co_n clusters composed of n Co atoms. The findings revealed that the binding energy (E_{b-Co₅/SiO₂(001)}) of Co₅/SiO₂(001) was the highest at 1.88 eV, suggesting that the Co₅ cluster exhibits the greatest stability when interfaced with the SiO₂(001). A direct linear correlation (y=0.11x-0.23) was observed in the connection between E_{b-Co_n/SiO₂(001)} and the average Bader charge (Q_ave-Bader) of the Co_n/SiO₂(001). The greater Q_ave-Bader value transferred between the Co_n clusters and the SiO₂ support, the stronger the binding and the higher the structural stability. As the Co_n cluster size increased, the d band center gradually moved away from the Fermi level, with the d band center energy for the Co₅/SiO₂(001) being the lowest at -0.96 eV. The most favorable reaction pathway for CO activation on the Co₃/SiO₂(001) is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.39 eV, whereas for Co₅/SiO₂(001), the optimal path is CO*→C*+O*, with an effective energy barrier of 1.19 eV, and Co₅ cluster, the optimal path is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.72 eV. Notably, the introduction of Co₅ clusters onto the hydroxylated SiO₂ surface proves to be more conducive to the activation of CO. By employing differential charge analysis and crystal orbital hamilton population (COHP) calculations, it was discernible that in the Co₃/SiO₂(001)-CO, Co₅/SiO₂(001)-CO and Co₅-CO, the transfer of electrons from Co to C amounted to 0.20, 0.15, and 0.24, respectively, the integrated COHP (ICOHP) values for the Co—C bond were -1.46, -0.91, and -1.70 eV, respectively, which are indicated a more robust interaction between C and Co in Co₅-CO and Co₃/SiO₂(001)-CO compared to Co₅/SiO₂(001)-CO. Notably, the intense interaction between CO and Co in the latter hinders the activation of CO.
- Co_n cluster,
- SiO₂(001),
- CO activity,
- electronic property
1. [1]
  SCHULZ H. Short history and present trends of Fischer-Tropsch synthesis[J]. Appl. Catal. A‒Gen., 1999,186:3-12. doi: 10.1016/S0926-860X(99)00160-X
2. [2]
  DE KLERK A. Thermal upgrading of Fischer-Tropsch olefins[J]. Energy Fuels, 2005,19:1462-1467. doi: 10.1021/ef050049w
3. [3]
  BRADY R C, PETTIT R. Mechanism of the Fischer-Tropsch reaction. The chain propagation step[J]. J. Am. Chem. Soc., 1981,103:1287-1289. doi: 10.1021/ja00395a081
4. [4]
  IGLESIA E. Design, synthesis, and use of cobalt-based Fischer-Tropsch synthesis catalysts[J]. Appl. Catal. A‒Gen., 1997,161:59-78. doi: 10.1016/S0926-860X(97)00186-5
5. [5]
  DEN OTTER J H, NIJVELD S R, DE JONG K P. Synergistic promotion of Co/SiO₂ Fischer-Tropsch catalysts by niobia and platinum[J]. ACS Catal., 2016,6:1616-1623. doi: 10.1021/acscatal.5b02418
6. [6]
  SUBRAMANIAN V, CHENG K, LANCELOT C, SVETLANA H, SéBASTIEN P, SIMONA M, OVIDIU E, MAYA M, VITALY V O, ANDREI Y K. Nanoreactors: An efficient tool to control the chain-length distribution in Fischer-Tropsch synthesis[J]. ACS Catal., 2016,6:1785-1792. doi: 10.1021/acscatal.5b01596
7. [7]
  DONG C, LI R T, QU Z P, FAN Y M, WANG J Y, DU X Z, LIU C X, FENG X H, NING Y X, MU R T, FU Q, BAO X H. Oxide support inert in its interaction with metal but active in its interaction with oxide and vice versa[J]. J. Am. Chem. Soc., 2025,147(16):13210-13219. doi: 10.1021/jacs.4c17075
8. [8]
  RENATA S, KAROLINA A C, PAWEL M, JACEK R, YANNICK M, LAETITIA V, SANDRA C, STANISLAW D. Fischer-Tropsch reaction on Co-containing microporous and mesoporous beta zeolite catalysts: The effect of porous size and acidity[J]. Catal. Today, 2020,354:109-122. doi: 10.1016/j.cattod.2019.05.004
9. [9]
10. [10]
  BEPARI S, LI X, ABROKWAH R, MOHAMMAD N, ARSLAN M, KUILA D. Co-Ru catalysts with different composite oxide supports for fischer-tropsch studies in 3D-printed stainless steel microreactors[J]. Appl. Catal. A‒Gen., 2020,608117838. doi: 10.1016/j.apcata.2020.117838
11. [11]
  OHYAMA J, ABE D, HIRAYAMA A, IWAI H, TSUCHIMURA Y, SAKAMOTO K, IRIKURA M, NAKAMURA Y, YOSHIDA H, MACHIDA M, NISHIMURA S, YAMAMOTO T, MATSUMURA S, TAKAHASHI K. Selective oxidation of methane to formaldehyde over a silica-supported cobalt single-atom catalyst[J]. J. Phys. Chem. C, 2022,126:1785-1792. doi: 10.1021/acs.jpcc.1c08739
12. [12]
  SAIB A M, CLAEYS M, VAN STEEN E. Silica supported cobalt Fischer-Tropsch catalysts: Effect of pore diameter of support[J]. Catal. Today, 2002,71(3/4):395-402.
13. [13]
  ELBASHIR N O, DUTTA P, MANIVANNAN A, SEEHRA M S, ROBERTS C B. Impact of cobalt-based catalyst characteristics on the performance of conventional gas-phase and supercritical-phase Fischer-Tropsch synthesis[J]. Appl. Catal. A‒Gen., 2005,285:169-180. doi: 10.1016/j.apcata.2005.02.023
14. [14]
  KRESSE G, FURTHMüLLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Comp. Mater. Sci., 1996,6:15-50. doi: 10.1016/0927-0256(96)00008-0
15. [15]
  KRESSE G, FURTHMüLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys. Rev. B, 1996,54:11169-11186. doi: 10.1103/PhysRevB.54.11169
16. [16]
  BLOCH P E. Projector augmented-wave method[J]. Phys. Rev. B, 1994,50:17953-17979. doi: 10.1103/PhysRevB.50.17953
17. [17]
  KRESSE G. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Phys. Rev. B, 1999,59:1758-1775.
18. [18]
  PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Phys. Rev. Lett., 1996,77:3865-3868. doi: 10.1103/PhysRevLett.77.3865
19. [19]
  HENKELMAN G, JóNSSON H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points[J]. J. Chem. Phys., 2000,113:9978-9985. doi: 10.1063/1.1323224
20. [20]
  MAO F, GAO C, WANG F, ZHANG C, ZHANG F S. Ab initio study of ferromagnetism induced by electronic hole localization in Al-doped α-SiO₂[J]. J. Phys. Chem. C, 2017,121:23055-23061. doi: 10.1021/acs.jpcc.7b06680
21. [21]
  WANG H, CHAI Z F, WANG D Q. Adsorption of uranyl on hydroxylated α-SiO₂(001): A first-principle study[J]. Dalton. Trans., 2015,44:1646-1654. doi: 10.1039/C4DT02872D
22. [22]
  LIU P, WANG Q S, LI X, ZHANG C C. Investigation of the states of water and OH groups on the surface of silica[J]. Colloid. Surf. Physicochem. Eng. Asp., 2009,334:112-115. doi: 10.1016/j.colsurfa.2008.10.028
23. [23]
  MURASHOV V V. Reconstruction of pristine and hydrolyzed quartz surfaces[J]. J. Phys. Chem. B, 2005,109:4144-4151. doi: 10.1021/jp0402075
24. [24]
  RUBAN A, HAMMER B, STOLTZE P, SKRIVER H L, NóRSKOV J K. Surface electronic structure and reactivity of transition and noble metals[J]. J. Mol. Catal. A‒Chem, 1997,115(3):421-429. doi: 10.1016/S1381-1169(96)00348-2
25. [25]
  HAMMER B, NORSKOV J K. Why gold is the noblest of all the metals[J]. Nature, 1995,376(6537):238-240. doi: 10.1038/376238a0
26. [26]
  HUO C F, LI Y W, WANG J G, JIAO H J. Formation of CH_x species from CO dissociation on double-stepped Co(0001): Exploring fischer-tropsch mechanism[J]. J. Phys. Chem. C, 2008,112:14108-14116.
27. [27]
  ZHANG R, LIU F, WANG Q, WANG B J, LI D B. Insight into CH_x formation in Fischer-Tropsch synthesis on the hexahedron Co catalyst: Effect of surface structure on the preferential mechanism and existence form[J]. Appl. Catal. A‒Gen., 2016,525:76-84. doi: 10.1016/j.apcata.2016.07.007
28. [28]
  HERRANZ T, DENG X Y, CABOT A, GUO J G, SALMERON M. Influence of the cobalt particle size in the CO hydrogenation reaction studied by in situ X-ray absorption spectroscopy[J]. J. Phys. Chem. B, 2009,113(31):10721-10727. doi: 10.1021/jp901602s
29. [29]
  TUXEN A, CARENCO S, CHINTAPALLI M, CHUANG C H, ESCUDERO C, PACH E, JIANG P, BORONDICS F, BEBERWYCK B, ALIVISATOS A P, THORNTON G, PONG W F, GUO J H, PEREZ R, BESENBACHER F, SALMERON M. Size-dependent dissociation of carbon monoxide on cobalt nanoparticles[J]. J. Am. Chem. Soc., 2013,135(6):2273-2278. doi: 10.1021/ja3105889
30. [30]
  BEZEMER G L, BITTER J H, KUIPERS H P C E, OOSTERBEEK H, HOLEWIjN J E, XU X D, KAPTEIjN F, DILLEN A J, DE JONG K P. Cobalt particle size effects in the Fischer-Tropsch reaction studied with carbon nanofiber supported catalysts[J]. J. Am. Chem. Soc., 2006,128(12):3956-3964. doi: 10.1021/ja058282w
31. [31]
  ZHAO J J, QUAN X, CHEN S, LIU Y M, YU H T. Cobalt nanoparticles encapsulated in porous carbons derived from core‐shell ZIF67@ZIF8 as efficient electrocatalysts for oxygen evolution reaction[J]. ACS Appl. Mater. Interfaces, 2017,9(34):28685-28694. doi: 10.1021/acsami.7b10138
32. [32]
  QIN C, HOU B, WANG J G, WANG G, MA Z Y, JIA L T, LI D B. Stabilizing optimal crystalline facet of cobalt catalysts for Fischer-Tropsch synthesis[J]. ACS Appl. Mater. Interfaces, 2019,11(37):33886-33893. doi: 10.1021/acsami.9b10174
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沈阳化工大学材料科学与工程学院沈阳 110142

Metal-support interaction effects on CO activation over Con/SiO2 catalysts

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通讯作者: 陈斌, bchen63@163.com

Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts