Progress in the thermo-catalytic hydrogenation of CO<sub>2</sub> to ethanol

MAO Yu-zhong; ZHA Fei; TIAN Hai-feng; TANG Xiao-hua; CHANG Yue; GUO Xiao-jun

doi:10.1016/S1872-5813(22)60065-3

Volume 51 Issue 10

Oct. 2023

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2023 > 51(10): 1514-1528

MAO Yu-zhong, ZHA Fei, TIAN Hai-feng, TANG Xiao-hua, CHANG Yue, GUO Xiao-jun. Progress in the thermo-catalytic hydrogenation of CO2 to ethanol[J]. Journal of Fuel Chemistry and Technology, 2023, 51(10): 1514-1528. doi: 10.1016/S1872-5813(22)60065-3

Citation:

MAO Yu-zhong, ZHA Fei, TIAN Hai-feng, TANG Xiao-hua, CHANG Yue, GUO Xiao-jun. Progress in the thermo-catalytic hydrogenation of CO₂ to ethanol[J]. Journal of Fuel Chemistry and Technology, 2023, 51(10): 1514-1528. doi: 10.1016/S1872-5813(22)60065-3

Citation:

PDF( 8726 KB)

Progress in the thermo-catalytic hydrogenation of CO₂ to ethanol

doi: 10.1016/S1872-5813(22)60065-3

College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

Funds: The project was supported by National Natural Science Foundation of China (22268039, 21865031)

Received Date: 2022-09-16
Accepted Date: 2022-10-16
Rev Recd Date: 2022-10-08

Available Online: 2022-10-24

Publish Date: 2023-10-10

Abstract

Abstract

The chemical conversion of CO₂ is considered as one of the effective measures to reduce carbon emission, where breakthroughs have been made in the thermo-catalytic hydrogenation of CO₂ to ethanol in recent years. However, the synthesis of ethanol from CO₂ still suffers from some problems such as low ethanol yield and abundant by-products. In this paper, the research progress made in the thermo-catalytic hydrogenation of CO₂ to ethanol was reviewed. The performance of various catalysts with zeolites, metal oxides, perovskites, silica, organic frameworks and carbon-based materials as the support was evaluated and the synergistic effect of different metals on the CO₂ conversion and the intervention of various active species on the reaction were analyzed. Accordingly, the catalyst systems that can effectively promote the adsorption and activation of CO₂ and the coupling of C–C bond were summarized. Finally, the appropriate conditions as well as possible reaction mechanism for the CO₂ hydrogenation to ethanol were proposed. The insight shown in this paper should be beneficial to designing efficient catalysts, optimizing the reaction conditions and understanding the mechanism of CO₂ hydrogenation to ethanol in the future.
- carbon dioxide hydrogenation,
- ethanol,
- catalyst,
- reaction mechanism

FullText(HTML)

References(72)

References

[1]	ZHANG S, WU Z X, LIU X F, HUA K M, SHAO Z L, WEI B Y, HUANG C J, WANG H, SUN Y H. A Short review of recent advances in direct CO₂ hydrogenation to alcohols[J]. Top Catal, 2021, 64(5/6): 371–394.
[2]	LU F X, CHEN X, WANG W, ZHANG Y. Adjusting the CO₂ hydrogenation pathway via the synergic effects of iron carbides and iron oxides[J]. Catal Sci Technol,2021,11(23):7694−7703. doi: 10.1039/D1CY01758F
[3]	PATRIZIO P, FAJARDY M, BUI M, DOWELL N M. CO₂ mitigation or removal: The optimal uses of biomass in energy system decarbonization[J]. Science,2021,24(7):102765. doi: 10.1016/j.isci.2021.102765
[4]	BEDIAKO B A, QIAN Q L, HAN B X. Synthesis of C_{2 +} chemicals from CO₂ and H₂ via C–C bond formation[J]. Accounts Chem Res,2021,54(10):2467−2476. doi: 10.1021/acs.accounts.1c00091
[5]	王桂硕. CO₂加氢制乙醇催化剂的结构构建及反应机理研究[D]. 天津: 天津大学, 2019. WANG Gui-shuo. Study on structural construction and reaction mechanism of catalyst for CO₂ hydrogenation to ethanol[D]. Tianjin: Tianjin University, 2019.
[6]	INUI T, YAMAMOTO T, INOUE M, HARA H, TAKEGUCHI T, KIM J B. Highly effective synthesis of ethanol by CO₂-hydrogenation on well balanced multi-functional FT-type composite catalysts[J]. Appl Catal A: Gen, 1998, 186 (1/2): 395–406.
[7]	STRANGES A. History of the Fischer-Tropsch synthesis in Germany 1926–45[J]. Stud Surf Sci Catal,2007,163(7):1−27.
[8]	STEINBERG M. History of CO₂ greenhouse gas mitigation technologies[J]. Energy Convers Manage, 1992, 33 (5–8): 311–315.
[9]	DING L P, SHI T T, GU J, CUI Y, ZHANG Z Y, YANG C J, CHEN T, LIN M, WANG P, XUE N H, PENG L M, GUO X F, ZHU Y, CHEN Z X, DING W P. CO₂ hydrogenation to ethanol over Cu@Na-Beta[J]. Chem,2020,6(10):2673−2689. doi: 10.1016/j.chempr.2020.07.001
[10]	ZHANG J W, SEWELL C, HUANG H W, LIN Z Q. Closing the anthropogenic chemical carbon cycle toward a sustainable future via CO₂ valorization[J]. Adv Energy Mater,2021,11(47):2102767. doi: 10.1002/aenm.202102767
[11]	DONALDSON L. 2D molecular sieve with range of uses[J]. Mater Today,2022,55:2−3. doi: 10.1016/j.mattod.2022.05.005
[12]	PUJADÓ P R, RABÓ J A, ANTOS G J, GEMBICKI S A. Industrial catalytic applications of molecular sieves[J]. Catal Today,1992,13(1):113−141. doi: 10.1016/0920-5861(92)80191-O
[13]	CHEN Y, ZHU X X, WANG X P, SU Y P. A reliable protocol for fast and facile constructing multi-hollow silicalite-1 and encapsulating metal nanoparticles within the hierarchical zeolite[J]. Chem Eng J,2021,419:129641. doi: 10.1016/j.cej.2021.129641
[14]	WANG C T, ZHANG J, QIN G Q, WANG L, ZUIDEMA E, YANG Q, DANG S H, YANG C G, XIAO J P, MENG X J, MESTERS C, XIAO F S. Direct conversion of syngas to ethanol within zeolite crystals[J]. Chem,2020,6(3):646−657. doi: 10.1016/j.chempr.2019.12.007
[15]	REGALADOVERA C, MANAVI N, ZHOU Z. Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO₂ hydrogenation[J]. Chem Eng J,2021,426:131767. doi: 10.1016/j.cej.2021.131767
[16]	ZHANG M H, YAO R, JIANG H X, LI G M, CHEN Y F. Insights into the mechanism of acetic acid hydrogenation to ethanol on Cu (111) surface[J]. Appl Surf Sci,2017,412:342−349. doi: 10.1016/j.apsusc.2017.03.222
[17]	HU S L, LI W. Sabatier principle of metal-support interaction for design of ultrastable metal nanocatalysts[J]. Science,2021,374(6573):1360−1365. doi: 10.1126/science.abi9828
[18]	YANG C S, MU R T, WANG G S, SONG J M, TIAN H, ZHAO Z J, GONG J L. Hydroxyl-mediated ethanol selectivity of CO₂ hydrogenation[J]. Chem Sci,2019,10:3161−3167. doi: 10.1039/C8SC05608K
[19]	佟小萌, 韩松洺. 负载型金属纳米催化剂对催化反应性能影响的研究进展[J]. 云南化工,2021,48(5):12−13. doi: 10.3969/j.issn.1004-275X.2021.05.05 TONG Xiao-meng, HAN Song-ming. Research progress on the effect of supported metal nano-catalysts on catalytic reaction performance[J]. Yunnan ChemTechnol,2021,48(5):12−13. doi: 10.3969/j.issn.1004-275X.2021.05.05
[20]	BAI S X, SHAO Q, WANG P T, DAI Q G, WANG X Y, HUANG X Q. Highly active and selective hydrogenation of CO₂ to ethanol by ordered Pd-Cu nanoparticles[J]. J Am Chem Soc,2017,139(20):6827−6830. doi: 10.1021/jacs.7b03101
[21]	ZHENG J N, AN K, WANG J M, LI J, LIU Y. Direct synthesis of ethanol via CO₂ hydrogenation over the Co/La-Ga-O composite oxide catalyst[J]. J Fuel Chem Technol,2019,47(6):697−708. doi: 10.1016/S1872-5813(19)30031-3
[22]	WANG D, BI Q Y, YIN G H, ZHAO W L, HUANG F Q, XIE X M, JIANG M H. Direct synthesis of ethanol via CO₂ hydrogenation using supported gold catalysts[J]. Chem Commun,2016,52(99):14226−14229. doi: 10.1039/C6CC08161D
[23]	LOU Y, JIANG F, ZHU W, WANG L, YAO T Y, WANG S S, YANG B, YANG B, ZHU Y F, LIU X H. CeO₂ supported Pd dimers boosting CO₂ hydrogenation to ethanol[J]. Appl Catal B: Environ,2021,291:120122. doi: 10.1016/j.apcatb.2021.120122
[24]	YE X, YANG C Y, PAN X L, MA J G, ZHANG Y R, REN Y J, LIU X Y, LI L, HUANG Y Q. Highly selective hydrogenation of CO₂ to ethanol via designed bifunctional Ir₁-In₂O₃ single-atom catalyst[J]. J Am Chem Soc,2020,142(45):19001−19005. doi: 10.1021/jacs.0c08607
[25]	WEI J, YAO R W, HAN Y, GE Q J, SUN J. Towards the development of the emerging process of CO₂ heterogenous hydrogenation into high-value unsaturated heavy hydrocarbons[J]. Chem Soc Rev,2021,50(19):10764−10805. doi: 10.1039/D1CS00260K
[26]	XU M J, LIU X L, SONG G Y, CAI Y Y, SHI B F, LIU Y T, DING X X, YANG Z X, TIAN P F, CAO C X, XU J. Regulating iron species compositions by Fe-Al interaction in CO₂ hydrogenation[J]. J Catal,2022,413:331−341. doi: 10.1016/j.jcat.2022.06.030
[27]	DU H, ZHU H J, LIU T, ZHAO Z A, CHEN X K, DONG W D, LU W, LUO W T, DING Y J. Higher alcohols synthesis via CO hydrogenation on Fe-promoted Co/AC catalysts[J]. Catal Today,2017,281:549−558. doi: 10.1016/j.cattod.2016.05.023
[28]	XU D, YANG H Q, HONG X L, LIU G L, TSANG S C E. Tandem catalysis of direct CO₂ hydrogenation to higher alcohols[J]. ACS Catal,2021,11(15):8978−8984. doi: 10.1021/acscatal.1c01610
[29]	WANG Y Q, ZHANG X X, HONG X L, LIU G L. Sulfate-promoted higher alcohol synthesis from CO₂ hydrogenation[J]. ACS Sustainable Chem Eng,2022,10(27):8980−8987. doi: 10.1021/acssuschemeng.2c02743
[30]	WANG K, HAN C, SHAO Z P, QIU J H, WANG S B, LIU S M. Perovskite oxide catalysts for advanced oxidation reactions[J]. Adv Funct Mater,2021,31:2102089. doi: 10.1002/adfm.202102089
[31]	HOU Y H, WANG X Y, CHEN M, GAO X Y, LIU Y Z, GUO Q J. Sr_1-xK_xFeO₃ perovskite catalysts with enhanced RWGS reactivity for CO₂ hydrogenation to light olefins[J]. Atmosphere,2022,13(5):760. doi: 10.3390/atmos13050760
[32]	AN K, ZHANG S R, WANG J M, LIU Q, ZHANG Z Y, LIU Y. A highly selective catalyst of Co/La₄Ga₂O₉ for CO₂ hydrogenation to ethanol[J]. J Energy Chem,2021,56:486−495. doi: 10.1016/j.jechem.2020.08.045
[33]	KUSAMA H, OKABE K, SAYAMA K, ARAKAWA H. CO₂ hydrogenation to ethanol over promoted Rh/SiO₂ catalysts[J]. Catal Today,1996,28:261−266. doi: 10.1016/0920-5861(95)00246-4
[34]	KUSAMA H, OKABE K, SAYAMA K, ARAKAWA H. Ethanol synthesis by catalytic hydrogenation of CO₂ over Rh-Fe/SiO₂ catalysts[J]. Energy,1997,22:343−348. doi: 10.1016/S0360-5442(96)00095-3
[35]	刘启予, 范炜. 介孔分子筛制备技术新进展——二次合成、超分子自组装和介孔生成剂法(英文)[J]. 高等学校化学学报,2021,42(1):60−73. LIU Qi-yu, FAN Wei. Recent advances in the synthesis of mesoporous zeolites by post-synthetic method, supramolecular self-assembly and mesopore generation agent[J]. Chem J Chin Univ,2021,42(1):60−73.
[36]	SHAWABKEH R, FAQIR N, RAWAJFEH K, HUSSIEN I A, HAMZA A. Adsorption of CO₂ on Cu/SiO₂ nano-catalyst: Experimental and theoretical study[J]. Appl Surf Sci,2022,586:152726. doi: 10.1016/j.apsusc.2022.152726
[37]	GORYACHEV A, PUSTOVARENKO A, SHETRK G, ALHAJRI N S, JAMAL A, ALBUALI M, KOPPEN L, KHAN S, RUSSKIKB A, RAMIREZ A, SHOINKHOROVA T, HENSEN E, GASCON J. A multi-parametric catalyst screening for CO₂ hydrogenation to ethanol[J]. ChemCatChem,2021,13(14):3324−3332. doi: 10.1002/cctc.202100302
[38]	AN K, ZHANG S, WANG H, LI N Y, ZHANG Z Y, LIU Y. Co⁰-Co^{δ +} active pairs tailored by Ga-Al-O spinel for CO₂-to-ethanol synthesis[J]. Chem Eng J,2022,433:134606. doi: 10.1016/j.cej.2022.134606
[39]	LI X L, YANG G H, ZHANG M, GAO X F, XIE H J, BAI Y X, WU Y Q, PAN J X, TAN Y S. Insight into the correlation between Cu species evolution and ethanol selectivity in the direct ethanol synthesis from CO hydrogenation[J]. ChemCatChem,2019,11(3):1123−1130. doi: 10.1002/cctc.201801888
[40]	ZHANG Q, WANG S, DONG M, FAN W B. CO₂ hydrogenation on metal-organic frameworks-based catalysts: A mini review[J]. Front Chem,2022,10:956223. doi: 10.3389/fchem.2022.956223
[41]	QIN Z, LI H, YANG X F, CHEN L Y, LI Y W, SHEN K. Heterogenizing homogeneous cocatalysts by well-designed hollow MOF-based nanoreactors for efficient and size-selective CO₂ fixation[J]. Appl Catal B: Environ,2022,307:121163. doi: 10.1016/j.apcatb.2022.121163
[42]	LU X F, LIU Y, HE Y R, KUHN A N, SHIH P C, SUN C J, WEN X D, SHI C, YANG H. Cobalt-based nonprecious metal catalysts derived from metal-organic frameworks for high-rate hydrogenation of carbon dioxide[J]. ACS Appl Mater Inter,2019,11(31):27717−27726. doi: 10.1021/acsami.9b05645
[43]	ZENG L, CAO Y, LI Z, DAI Y H, WANG Y K, AN B, ZHANG J Z, LI H, ZHOU Y, LIN W B, WANG C. Multiple cuprous centers supported on a titanium-based metal-organic framework catalyze CO₂ hydrogenation to ethylene[J]. ACS Catal,2021,11(18):11696−11705. doi: 10.1021/acscatal.1c01939
[44]	GUTTEROD E, LAZZARINI A, FJERMESTAD T, KAUR G, MANZOLI M, BORDIGA S, SVELLE S, LILLERUD K P, SKULASON E, ØIEN S, NOVA A, OLSBYE U. Hydrogenation of CO₂ to methanol by Pt nanoparticles encapsulated in UiO-67: Deciphering the role of the metal-organic framework[J]. J Am Chem Soc,2020,142(2):999−1009. doi: 10.1021/jacs.9b10873
[45]	FAN Y, ZHANG J, SHEN Y, ZHENG B, ZHANG W N, HUO F W. Emerging porous nanosheets: From fundamental synthesis to promising applications[J]. Nano Res,2021,14:1−28. doi: 10.1007/s12274-020-3082-4
[46]	CHOE K, ZHENG F B, WANG H, YUAN Y, ZHAO W S, XUE G G, QIU X Y, RI X, SHI X H, WANG Y L, LI G D, TANG Z Y. Fast and selective semihydrogenation of alkynes by palladium nanoparticles sandwiched in metal-organic frameworks[J]. Angew Chem Int Ed,2020,59:3650−3657. doi: 10.1002/anie.201913453
[47]	SHAO S X, CUI C Q, TANG Z Y, LI G D. Recent advances in metal-organic frameworks for catalytic CO₂ hydrogenation to diverse products[J]. Nano Res, 2022, 15(12): 10110−10133.
[48]	NIU T C. Old materials with new properties II: the metal carbides[J]. Nano Today,2018,18:12−14. doi: 10.1016/j.nantod.2017.10.001
[49]	ZHANG H Y, HAN H, XIAO L F, WU W. Highly selective synthesis of ethanol via CO₂ hydrogenation over CoMoC_x catalysts[J]. ChemCatChem,2021,13(14):3333−3339. doi: 10.1002/cctc.202100204
[50]	YE X, MA J G, YU W G, PAN X L, YANG C Y, WANG C, LIU Q G, HUANG Y Q. Construction of bifunctional single-atom catalysts on the optimized β-Mo₂C surface for highly selective hydrogenation of CO₂ into ethanol[J]. J Energy Chem,2022,67:184−192. doi: 10.1016/j.jechem.2021.10.017
[51]	高钊. 改性蒙脱土负载钴催化剂浆态床费—托合成反应性能的研究[D]. 西安: 陕西师范大学, 2017. GAO Zhao. Performance study of modified montmorillonite-loaded cobalt catalyst slurry bed Fischer-Tropsch synthesis reaction[D]. Xian: Shaanxi Normal University, 2017.
[52]	ZHOU H, CHEN Z X, KOUNTOUPI E, TSOUKALOU A, ABDALA P M, FLORIAN P, FEDOROV A, MULLER C R. Two-dimensional molybdenum carbide 2D-Mo₂C as a superior catalyst for CO₂ hydrogenation[J]. Nat Commun,2021,12(1):5510. doi: 10.1038/s41467-021-25784-0
[53]	LI Z, WU Y. 2D early transition metal carbides (MXenes) for catalysis[J]. Small,2019,15(29):e1804736. doi: 10.1002/smll.201804736
[54]	CAPARROS F, SOLER L, ROSSELL M, ANGURELL I, PICCOLO L, ROSSELL O, LLORCA J. Remarkable carbon dioxide hydrogenation to ethanol on a palladium/iron oxide single-atom catalyst[J]. ChemCatChem,2018,10(11):2365−2369. doi: 10.1002/cctc.201800362
[55]	WANG L X, WANG L, ZHANG J, LIU X L, WANG H, ZHANG W, YANG Q, MA J Y, DONG X, YOO S J, KIM J G, MENG X J, XIAO F S. Selective hydrogenation of CO₂ to ethanol over cobalt catalysts[J]. Angew Chem Int Ed,2018,57(21):6104−6108. doi: 10.1002/anie.201800729
[56]	ALI S, ALI S, TABASSUM N. A review on CO₂ hydrogenation to ethanol: Reaction mechanism and experimental studies[J]. J Environ Chem Eng,2022,10(1):106962. doi: 10.1016/j.jece.2021.106962
[57]	KIM J, LEE S, LEE S B, CHOI M J, LEE K W. Performance of catalytic reactors for the hydrogenation of CO₂ to hydrocarbons[J]. Catal Today, 2006, 115(1/2/3/4): 228–234.
[58]	XU D, WANG Y Q, DING M Y, HONG X L, LIU G L, TSANG S C. Advances in higher alcohol synthesis from CO₂ hydrogenation[J]. Chem,2021,7(4):849−881. doi: 10.1016/j.chempr.2020.10.019
[59]	HE Y M, LIU S L, FU W J, WANG C, MEBRAHTU C, SUN R Y, ZENG F. Thermodynamic analysis of CO₂ hydrogenation to higher alcohols (C₂₋₄OH): Effects of isomers and methane[J]. ACS Omega,2022,7(19):16502−16514. doi: 10.1021/acsomega.2c00502
[60]	LI M, PHAM T, KO Y, ZHAO K, ZHONG L P, LUO W, ZUTTEL A. Support-dependent Cu-In bimetallic catalysts for tailoring the activity of reverse water gas shift reaction[J]. ACS Sustainable Chem Eng,2022,10(4):1524−1535. doi: 10.1021/acssuschemeng.1c06935
[61]	ZHENG X L, GUO L, LI W L, CAO Z R, LIU N Y, ZHANG Q, XING M M, SHI Y Y, GUO J. Insight into the mechanism of reverse water-gas shift reaction and ethanol formation catalyzed by Mo6S8-TM clusters[J]. Mol Catal,2017,439:155−162. doi: 10.1016/j.mcat.2017.06.030
[62]	CAO A, SCHUMANN J, WANG T, ZHANG L N, XIAO J P, BOTHRA P, LIU Y, ABILD P F, NORSKOV J K. Mechanistic insights into the synthesis of higher alcohols from syngas on CuCo alloys[J]. ACS Catal,2018,8(11):10148−10155. doi: 10.1021/acscatal.8b01596
[63]	LIU S H, YANG C S, ZHA S J, SHARAPA D, STUDT F, ZHAO Z J, GONG J L. Moderate surface segregation promotes selective ethanol production in CO₂ hydrogenation reaction over CoCu catalysts[J]. Angew Chem Int Ed,2022,61(2):e202109027.
[64]	CHEN W, FILOT I, PESTMAN R, HENSEN E J. Mechanism of cobalt-catalyzed CO hydrogenation: 2. Fischer-Tropsch synthesis[J]. ACS Catal,2017,7(12):8061−8071. doi: 10.1021/acscatal.7b02758
[65]	HE Z H, QIAN Q L, MA J, MENG Q L, ZHOU H C, SONG J L, LIU Z M, HAN B X. Water-enhanced synthesis of higher alcohols from CO₂ hydrogenation over a Pt/Co₃O₄ catalyst under milder conditions[J]. Angew Chem,2016,55:737−741. doi: 10.1002/anie.201507585
[66]	CHEN Y, CHOI S, THOMPSON L. Low temperature CO₂ hydrogenation to alcohols and hydrocarbons over Mo₂C sup-ported metal catalysts[J]. J Catal,2016,343:147−156. doi: 10.1016/j.jcat.2016.01.016
[67]	LIU G B, YANG G H, PENG X B, WU J H, TSUBAKI N. Recent advances in the routes and catalysts for ethanol synthesis from syngas[J]. Chem Soc Rev,2022,51(13):1460−4744.
[68]	ZHANG F Y, CHEN K, JIANG Q M, HE S, CHEN Q J, LIU Z M, KANG J C, ZHANG Q H, WANG Y. Selective transformation of methanol to ethanol in the presence of syngas over composite catalysts[J]. ACS Catal,2022,12(14):8451−8461. doi: 10.1021/acscatal.2c01725
[69]	FENG S Q, LIN X S, SONG X G, MEI B B, MU J L, LI J W, LIU Y, JIANG Z, DING Y J. Constructing efficient single Rh sites on activated carbon via surface carbonyl groups for methanol carbonylation[J]. ACS Catal,2021,11(2):682−690. doi: 10.1021/acscatal.0c03933
[70]	ZHOU W, KANG J C, CHENG K, HE S, SHI J Q, ZHOU C, ZHANG Q H, CHEN J C, PENG L M, CHEN M S, WANG Y. Direct conversion of syngas into methyl acetate, ethanol and ethylene by relay catalysis via dimethyl ether intermediate[J]. Angew Chem Int Ed,2018,57:12012. doi: 10.1002/anie.201807113
[71]	ZHANG F, CHEN Z Y, FANG X D, LIU H C, LIU Y, ZHU W L. Catalytic activity of Cu/ZnO catalysts mediated by MgO promoter in hydrogenation of methyl acetate to ethanol[J]. J Energy Chem,2021,61:203−209. doi: 10.1016/j.jechem.2021.03.028
[72]	WANG X L, RAMIREZ P, LIAO W J, RODRIGUEZ J, LIU P. Cesium-induced active sites for C−C coupling and ethanol synthesis from CO₂ hydrogenation on Cu/ZnO(0001̅) Surfaces[J]. J Am Chem Soc,2021,143(33):13103−13112. doi: 10.1021/jacs.1c03940