Siliceous mesocellular foam supported Cu catalysts for promoting non-thermal plasma activated CO₂ hydrogenation toward methanol synthesis

Abstract

Electrified non-thermal plasma (NTP) catalytic hydrogenation is the promising alternative to the thermal counterparts, being able to be operated under mild conditions and compatible with green electricity/hydrogen. Rational design of the catalysts for such NTP-catalytic systems is one of the keys to improve the process efficiency. Here, we present the development of siliceous mesocellular foam (MCF) supported Cu catalysts for NTP-catalytic CO₂ hydrogenation to methanol. The findings show that the pristine MCF support with high specific surface area and large mesopore of 784 m²·g⁻¹ and ~8.5 nm could promote the plasma discharging and the diffusion of species through its framework, outperforming other control porous materials (viz., silicalite-1, SiO₂, and SBA-15). Compared to the NTP system employing the bare MCF, the inclusion of Cu and Zn in MCF (i.e., Cu₁Zn₁/MCF) promoted the methanol formation of the NTP-catalytic system with a higher space-time yield of methanol at ~275 μmol·g_cat⁻¹·h⁻¹ and a lower energy consumption of 26.4 kJ·{\mathrm{m}\mathrm{m}\mathrm{o}\mathrm{l}}_{{\mathrm{C}\mathrm{H}}_3\mathrm{O}\mathrm{H}}⁻¹ (conversely, ~225 μmol·g_cat⁻¹·h⁻¹ and ~71 kJ·{\mathrm{m}\mathrm{m}\mathrm{o}\mathrm{l}}_{{\mathrm{C}\mathrm{H}}_3\mathrm{O}\mathrm{H}}⁻¹, respectively, for the bare MCF system at 10.1 kV). The findings suggest that inclusion of active metal sites (especially Zn species) could stabilize the CO₂/CO-related intermediates to facilitate the surface reaction toward methanol formation.

Graphical abstract

Keywords

non-thermal plasma (NTP) catalysis / Cu catalyst / CO₂ hydrogenation / methanol / siliceous mesocellular foam (MCF)

References

[1] Ou Y , Roney C , Alsalam J , Calvin K , Creason J , Edmonds J , Fawcett A A , Kyle P , Narayan K , O’Rourke P . . Deep mitigation of CO₂ and non-CO₂ greenhouse gases toward 1.5 degrees C and 2 degrees C futures. Nature Communications, 2021, 12(1): 6245

[2] Alamer A M , Ouyang M , Alshafei F H , Nadeem M A , Alsalik Y , Miller J T , Flytzani-Stephanopoulos M , Sykes E C H , Manousiouthakis V , Eagan N M . Design of dilute palladium-indium alloy catalysts for the selective hydrogenation of CO₂ to methanol. ACS Catalysis, 2023, 13(15): 9987–9996

[3] Saravanan A , Senthil Kumar P , Vo D V N , Jeevanantham S , Bhuvaneswari V , Anantha Narayanan V , Yaashikaa P R , Swetha S , Reshma B . A comprehensive review on different approaches for CO₂ utilization and conversion pathways. Chemical Engineering Science, 2021, 236: 116515

[4] Kim C , Yoo C-J , Oh H-S , Min B K , Lee U . Review of carbon dioxide utilization technologies and their potential for industrial application. Journal of CO₂ Utilization, 2022, 65: 102239

[5] Sun S , Sun H , Williams P T , Wu C . Recent advances in integrated CO₂ capture and utilization: a review. Sustainable Energy & Fuels, 2021, 5(18): 4546–4559

[6] Ye R P , Ding J , Gong W , Argyle M D , Zhong Q , Wang Y , Russell C K , Xu Z , Russell A G , Li Q , Fan M , Yao Y G . CO₂ hydrogenation to high-value products via heterogeneous catalysis. Nature Communications, 2019, 10(1): 5698

[7] Yang H , Zhang C , Gao P , Wang H , Li X , Zhong L , Wei W , Sun Y . A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons. Catalysis Science & Technology, 2017, 7(20): 4580–4598

[8] Meunier F C , Dansette I , Paredes-Nunez A , Schuurman Y . Cu-bound formates are main reaction intermediates during CO₂ hydrogenation to methanol over Cu/ZrO₂. Angewandte Chemie International Edition, 2023, 62(29): e202303939

[9] Lu B , Wu F , Li X , Luo C , Zhang L . Reconstruction of interface oxygen vacancy for boosting CO₂ hydrogenation by Cu/CeO₂ catalysts with thermal treatment. Carbon Capture Science & Technology, 2024, 10: 100–173

[10] Murthy P S , Wilson L , Zhang X , Liang W , Huang J . Ni-doped metal-azolate framework-6 derived carbon as a highly active catalyst for CO₂ conversion through the CO₂ hydrogenation reaction. Carbon Capture Science & Technology, 2023, 7: 100–104

[11] Snider J L , Streibel V , Hubert M A , Choksi T S , Valle E , Upham D C , Schumann J , Duyar M S , Gallo A , Abild-Pedersen F . . Revealing the synergy between oxide and alloy phases on the performance of bimetallic In-Pd catalysts for CO₂ hydrogenation to methanol. ACS Catalysis, 2019, 9(4): 3399–3412

[12] Zachopoulos A , Heracleous E . Overcoming the equilibrium barriers of CO₂ hydrogenation to methanol via water sorption: a thermodynamic analysis. Journal of CO₂ Utilization, 2017, 21: 360–367

[13] Xu S , Chen H , Fan X . Rational design of catalysts for non-thermal plasma (NTP) catalysis: a reflective review. Catalysis Today, 2023, 419: 114–144

[14] Zhang Y , Wang B , Ji Z , Jiao Y , Shao Y , Chen H , Fan X . Plasma-catalytic CO₂ methanation over NiFe_n/(Mg, Al)O_x catalysts: catalyst development and process optimisation. Chemical Engineering Journal, 2023, 465: 142855

[15] Sun Y , Wu J , Wang Y , Li J , Wang N , Harding J , Mo S , Chen L , Chen P , Fu M , Ye D , Huang J , Tu X . Plasma-catalytic CO₂ hydrogenation over a Pd/ZnO catalyst: in situ probing of gas-phase and surface reactions. JACS Au, 2022, 2(8): 1800–1810

[16] Kim D Y , Ham H , Chen X , Liu S , Xu H , Lu B , Furukawa S , Kim H H , Takakusagi S , Sasaki K , Nozaki T . Cooperative catalysis of vibrationally excited CO₂ and alloy catalyst breaks the thermodynamic equilibrium limitation. Journal of the American Chemical Society, 2022, 144(31): 14140–14149

[17] Wang Y , Yang W , Xu S , Zhao S , Chen G , Weidenkaff A , Hardacre C , Fan X , Huang J , Tu X . Shielding protection by mesoporous catalysts for improving plasma-catalytic ambient ammonia synthesis. Journal of the American Chemical Society, 2022, 144(27): 12020–12031

[18] Xu S , Chansai S , Stere C , Inceesungvorn B , Goguet A , Wangkawong K , Taylor S F R , Al-Janabi N , Hardacre C , Martin P A . . Sustaining metal-organic frameworks for water-gas shift catalysis by non-thermal plasma. Nature Catalysis, 2019, 2(2): 142–148

[19] Jin Q , Chen S , Meng X , Zhou R , Xu M , Yang M , Xu H , Fan X , Chen H . Methanol steam reforming for hydrogen production over Ni/ZrO₂ catalyst: comparison of thermal and non-thermal plasma catalysis. Catalysis Today, 2024, 425: 114360

[20] Vakili R , Gholami R , Stere C E , Chansai S , Chen H , Holmes S M , Jiao Y , Hardacre C , Fan X . Plasma-assisted catalytic dry reforming of methane (DRM) over metal-organic frameworks (MOFs)-based catalysts. Applied Catalysis B: Environmental, 2020, 260: 118–195

[21] Jiang X , Nie X , Guo X , Song C , Chen J G . Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis. Chemical Reviews, 2020, 120(15): 7984–8034

[22] Eliasson B , Kogelschatz U , Xue B , Zhou L M . Hydrogenation of carbon dioxide to methanol with a discharge-activated catalyst. Industrial & Engineering Chemistry Research, 1998, 37(8): 3350–3357

[23] Bill A , Eliasson B , Kogelschatz U , Zhou L M . Comparison of CO₂ hydrogenation in a catalytic reactor and in a dielectric-barrier discharge. Studies in Surface Science and Catalysis, 1998, 114: 541–544

[24] Wang L , Yi Y , Guo H , Tu X . Atmospheric pressure and room temperature synthesis of methanol through plasma-catalytic hydrogenation of CO₂. ACS Catalysis, 2018, 8(1): 90–100

[25] Cui Z , Meng S , Yi Y , Jafarzadeh A , Li S , Neyts E C , Hao Y , Li L , Zhang X , Wang X . . Plasma-catalytic methanol synthesis from CO₂ hydrogenation over a supported Cu cluster catalyst: insights into the reaction mechanism. ACS Catalysis, 2022, 12(2): 1326–1337

[26] Men Y L , Liu Y , Wang Q , Luo Z H , Shao S , Li Y B , Pan Y X . Highly dispersed Pt-based catalysts for selective CO₂ hydrogenation to methanol at atmospheric pressure. Chemical Engineering Science, 2019, 200: 167–175

[27] Zhang X , Sun Z , Shan Y , Pan H , Jin Y , Zhu Z , Zhang L , Li K . Boosting methanol production via plasma catalytic CO₂ hydrogenation over a MnO_x/ZrO₂ catalyst. Catalysis Science & Technology, 2023, 13(8): 2529–2539

[28] Ronda-Lloret M , Wang Y , Oulego P , Rothenberg G , Tu X , Shiju N R . CO₂ hydrogenation at atmospheric pressure and low temperature using plasma-enhanced catalysis over supported cobalt oxide catalysts. ACS Sustainable Chemistry & Engineering, 2020, 8(47): 17397–17407

[29] Meng S , Wu L , Liu M , Cui Z , Chen Q , Li S , Yan J , Wang L , Wang X , Qian J , Guo H , Niu J , Bogaerts A , Yi Y . Plasma‐driven CO₂ hydrogenation to CH₃OH over Fe₂O₃/γ‐Al₂O₃ catalyst. AIChE Journal. American Institute of Chemical Engineers, 2023, 69(10): e18154

[30] Michiels R , Engelmann Y , Bogaerts A . Plasma catalysis for CO₂ hydrogenation: unlocking new pathways toward CH₃OH. Journal of Physical Chemistry C, 2020, 124(47): 25859–25872

[31] WangJZhangKBogaertsAMeynenV. 3D porous catalysts for plasma-catalytic dry reforming of methane: how does the pore size affect the plasma-catalytic performance? Chemical Engineering Journal, 2023, 464: 142574

[32] Daoura O , Kaydouh M-N , El-Hassan N , Massiani P , Launay F , Boutros M . Mesocellular silica foam-based Ni catalysts for dry reforming of CH₄ (by CO₂). Journal of CO₂ Utilization, 2018, 24: 112–119

[33] Yan X , Zhang L , Zhang Y , Qiao K , Yan Z , Komarneni S . Amine-modified mesocellular silica foams for CO₂ capture. Chemical Engineering Journal, 2011, 168(2): 918–924

[34] Bai P , Zhao Z , Zhang Y , He Z , Liu Y , Wang C , Ma S , Wu P , Zhao L , Mintova S . . Rational design of highly efficient PdIn-In₂O₃ interfaces by a capture-alloying strategy for benzyl alcohol partial oxidation. ACS Applied Materials & Interfaces, 2023, 15(15): 19653–19664

[35] Wu P , Cao Y , Zhao L , Wang Y , He Z , Xing W , Bai P , Mintova S , Yan Z . Formation of PdO on Au-Pd bimetallic catalysts and the effect on benzyl alcohol oxidation. Journal of Catalysis, 2019, 375: 32–43

[36] Wang S , Song L , Qu Z . Cu/ZnAl₂O₄ catalysts prepared by ammonia evaporation method: improving methanol selectivity in CO₂ hydrogenation via regulation of metal-support interaction. Chemical Engineering Journal, 2023, 469: 144008

[37] Kuld S , Thorhauge M , Falsig H , Elkjær C F , Helveg S , Chorkendorff I , Sehested J . Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis. Science, 2016, 352(6288): 969–974

[38] Turco M , Bagnasco G , Cammarano C , Senese P , Costantino U , Sisani M . Cu/ZnO/Al₂O₃ catalysts for oxidative steam reforming of methanol: the role of Cu and the dispersing oxide matrix. Applied Catalysis B: Environmental, 2007, 77(1-2): 46–57

[39] Arena F , Giovenco R , Torre T , Venuto A , Parmaliana A . Activity and resistance to leaching of Cu-based catalysts in the wet oxidation of phenol. Applied Catalysis B: Environmental, 2003, 45(1): 51–62

[40] Xiao K , Wang Q , Qi X , Zhong L . For better industrial Cu/ZnO/Al₂O₃ methanol synthesis catalyst: a compositional study. Catalysis Letters, 2017, 147(6): 1581–1591

[41] Navarro-Jaén S , Virginie M , Thuriot-Roukos J , Wojcieszak R , Khodakov A Y . Structure-performance correlations in the hybrid oxide-supported copper-zinc SAPO-34 catalysts for direct synthesis of dimethyl ether from CO₂. Journal of Materials Science, 2022, 57(5): 3268–3279

[42] Xu S , Chansai S , Xu S , Stere C E , Jiao Y , Yang S , Hardacre C , Fan X . CO poisoning of Ru catalysts in CO₂ hydrogenation under thermal and plasma conditions: a combined kinetic and diffuse reflectance infrared fourier transform spectroscopy-mass spectrometry study. ACS Catalysis, 2020, 10(21): 12828–12840

[43] Chen H , Mu Y , Shao Y , Chansai S , Xu S , Stere C E , Xiang H , Zhang R , Jiao Y , Hardacre C . . Coupling non-thermal plasma with Ni catalysts supported on BETA zeolite for catalytic CO₂ methanation. Catalysis Science & Technology, 2019, 9(15): 4135–4145

[44] Chen H , Mu Y , Shao Y , Chansai S , Xiang H , Jiao Y , Hardacre C , Fan X . Nonthermal plasma (NTP) activated metal-organic frameworks (MOFs) catalyst for catalytic CO₂ hydrogenation. AIChE Journal, 2020, 66(4): e16853

[45] Zhang Q Z , Bogaerts A . Propagation of a plasma streamer in catalyst pores. Plasma Sources Science & Technology, 2018, 27(3): 035009

[46] Zhang Q Z , Bogaerts A . Plasma streamer propagation in structured catalysts. Plasma Sources Science & Technology, 2018, 27(10): 105013

[47] Kattel S , Ramírez P J , Chen J G , Rodriguez J A , Liu P . Active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts. Science, 2017, 355(6331): 1296–1299

[48] Yan Y , Wong R J , Ma Z , Donat F , Xi S , Saqline S , Fan Q , Du Y , Borgna A , He Q . . CO₂ hydrogenation to methanol on tungsten-doped Cu/CeO₂ catalysts. Applied Catalysis B: Environmental, 2022, 306: 121098

[49] Wang W , Qu Z , Song L , Fu Q . CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts: tuning methanol selectivity via metal-support interaction. Journal of Energy Chemistry, 2020, 40: 22–30

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This project has received funding from the International Science and Technology Cooperation Project of Innovative Supporting Plan from Jiangsu Provincial Department of Science and Technology (Grant No. BZ2022040), the National Natural Science Foundation of China (Grant No. 22278204), and the Jiangsu Specially-Appointed Professors Program. This Project was also partially supported by Ningbo Natural Science Foundation (Project ID 2023J245), the special innovation project fund (Grant No. XMGL-KJZX-202204, 52376207, 52276211) from the Institute of Wenzhou, Zhejiang University.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://doi.org/10.1007/s11705-024-2419-z and is accessible for authorized users.

RIGHTS & PERMISSIONS

2024 Higher Education Press