To address the challenge of low selectivity in CO2 hydrogenation to ethanol,Cu-Fe catalysts with different sodium loadings (xNaCuFe/ZnAl2O4) were prepared by the impregnation method.The effects of reaction temperature,reaction pressure,and space velocity on the catalytic performance were systematically examined.The results showed that the addition of sodium changed the electronic environment around the copper species,enhanced the metal-support interaction,and significantly increased the number of medium-strong basic sites on the catalyst surface.The CO2 conversion reached 33.55% and the space-time yield of ethanol was 78.20 mg/(gcat·h) under the reaction conditions of 350℃,3 MPa,and 6 000 mL/(gcat·h).Under the optimal reaction conditions [290℃,3.5 MPa,and 3000 mL/(gcat·h)],the CO2 conversion was 25.38%,with an ethanol selectivity of 16.35%.In situ DRIFTS results indicated that CO2 hydrogenation to ethanol on the prepared catalyst followed the CO-mediated mechanism:*CO couples with *CHx generated from its dissociation to form C2 oxygenated intermediates,which were subsequently hydrogenated to ethanol.
ZhouC, AitbekovaA, LiccardoG, et al. Steam-assisted selective CO2 hydrogenation to ethanol over Ru-In catalysts[J]. Angewandte Chemie International Edition, 2024, 63:e202406761.
[3]
DingL, ShiT, GuJ, et al. CO2 hydrogenation to ethanol over Cu@Na-Beta[J]. Chem, 2020, 6:2673-2689.
WangY, WangW, HeR, et al. Carbon-based electron buffer layer on ZnOx-Fe5C2-Fe3O4 boosts ethanol synthesis from CO2 hydrogenation[J]. Angewandte Chemie International Edition, 2023, 62(46):e202311786.
[6]
IrshadM, JoH, BibiS S, et al. Synthesis of selective C5+ paraffins directly from CO2 over Cu-Co catalyst:Dynamic role of Cu to establish the Fischer-Tropsch synthesis process[J]. Chemical Engineering Journal, 2025, 517:164291.
[7]
LiX, WangH, MaQ, et al. Na promotes selective hydrogenation of CO2 to ethanol over CoMnO catalysts[J]. Applied Catalysis B:Environment and Energy, 2026, 382:125998.
[8]
BibiS S, AhmedS, JoH, et al. Turning methanation into chain growth:Na-induced mechanistic bifurcation on Co-ZrOx catalyst[J]. Chinese Journal of Catalysis, 2026, 80:1-18.
[9]
ZhangS, WuZ, LiuX, et al. Tuning the interaction between Na and Co2C to promote selective CO2 hydrogenation to ethanol[J]. Applied Catalysis B:Environmental, 2021, 293:120207.
[10]
SongL, WangH, WangS, et al. Dual-site activation of H2 over Cu/ZnAl2O4 boosting CO2 hydrogenation to methanol[J]. Applied Catalysis B:Environmental, 2023, 322:122137.
[11]
SiddiquiH, ParraM R, QureshiM S, et al. Studies of structural,optical,and electrical properties associated with defects in sodium-doped copper oxide (CuO/Na) nanostructures[J]. Journal of Materials Science, 2018, 53(12):8826-8843.
[12]
NguyenP H, ShinE W. Disordered structure of ZnAl2O4 phase and the formation of a Zn NCO complex in ZnAl mixed oxide catalysts for glycerol carbonylation with urea[J]. Journal of Catalysis, 2019, 373:147-160.
[13]
ZhangQ, WangS, GengR, et al. Hydrogenation of CO2 to higher alcohols on an efficient Cr-modified CuFe catalyst[J]. Applied Catalysis B:Environmental, 2023, 337:123013.
[14]
KostyniukA, LikozarB. High-yield ethanol production via thermocatalytic CO2 hydrogenation over Cs/CuZnFe catalyst in a continuous flow reactor[J]. Chemical Engineering Journal, 2025, 520:166135.
[15]
YangQ, WangR, ZhangX, et al. Topotactic transformation of metal-organic frameworks to iron-based catalysts for the direct hydrogenation of CO2 to olefins[J]. Catalysis Science & Technology, 2023, 13(11):3258-3269.
[16]
MaY, PuX, LiuY, et al. Synergistic catalysis over Pd-Fe-Zn with triple-interface structures for selective CO2 hydrogenation to ethanol[J]. ACS Catalysis, 2025:18580-18590.
WangY, LiY, WangX, et al. Effects of redox mediators on α-Fe2O3 exposed by {012} and {104} facets for photocatalytic water oxidation[J]. Applied Catalysis B:Environmental, 2017, 206:216-220.
[19]
XuD, DingM, HongX, et al. Selective C2+ alcohol synthesis from direct CO2 hydrogenation over a Cs-promoted Cu-Fe-Zn catalyst[J]. ACS Catalysis, 2020, 10(9):5250-5260.
[20]
DongX, LiF, ZhaoN, et al. CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method[J]. Applied Catalysis B:Environmental, 2016, 191:8-17.
ZhaoQ, FanG, LiF. Unique CuO-FeO interfaces in Cu-decorated Fe-based catalysts facilitating CO2 hydrogenation to higher hydrocarbons[J]. Chemical Engineering Journal, 2024, 495:153309.
[23]
JiaX, ZhangX, RuiN, et al. Structural effect of Ni/ZrO2 catalyst on CO2 methanation with enhanced activity[J]. Applied Catalysis B:Environmental, 2019, 244:159-169.
[24]
HuangS, FangL, LuoS, et al. Tailoring electronic and interfacial synergy in Cu-FeGa/Al2O3 for direct CO2 hydrogenation to ethanol[J]. Chemical Engineering Journal, 2026, 531:173969.
[25]
BaiS, ShaoQ, WangP, et al. Highly active and selective hydrogenation of CO2 to ethanol by ordered Pd-Cu nanoparticles[J]. Journal of the American Chemical Society, 2017, 139(20):6827-6930.
[26]
ZhangD, VirchenkoV, JansenC, et al. Characterization of CO adsorbed to clean and partially oxidized Cu(211) and Cu(111)[J]. The Journal of Physical Chemistry C, 2023, 127:24158-24167.
[27]
WangS, ZhangL, WangP, et al. Highly effective conversion of CO2 into light olefins abundant in ethene[J]. Chem, 2022, 8:1376-1394.
[28]
WangY, XuD, ZhangX, et al. Selective C2+ alcohol synthesis by CO2 hydrogenation via a reaction-coupling strategy[J]. Catalysis Science & Technology, 2022, 12:1539-1550.
[29]
WangY, ZhangX, HongX, et al. Sulfate-promoted higher alcohol synthesis from CO2 hydrogenation[J]. ACS Sustainable Chemistry Engineering, 2022, 10:8980-8987.
[30]
OchoaJ V, TrevisanutC, MilletJ M, et al. In situ DRIFTS-MS study of the anaerobic oxidation of ethanol over spinel mixed oxides[J]. The Journal of Physical Chemistry C, 2013, 117:23908-23918.
PDF
(4340KB)
