{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T06:14:49Z","timestamp":1769148889694,"version":"3.49.0"},"reference-count":57,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2020,12,24]],"date-time":"2020-12-24T00:00:00Z","timestamp":1608768000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["Grant No. 21373152"],"award-info":[{"award-number":["Grant No. 21373152"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Frontier and Applied Basic Research of Chongqing","award":["Grant No. cstc2018jcyjAX0191"],"award-info":[{"award-number":["Grant No. cstc2018jcyjAX0191"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Unlike the usual method of COx (x = 1, 2) hydrogenation using H2 directly, H2S and HSiSH (silicon-activated H2S) were selected as alternative hydrogen sources in this study for the COx hydrogenation reactions. Our results suggest that it is kinetically infeasible for hydrogen in the form of H2S to transfer to COx at low temperatures. However, when HSiSH is employed instead, the title reaction can be achieved. For this approach, the activation of CO2 is initiated by its interaction with the HSiSH molecule, a reactive species with both a hydridic H\u03b4\u2212 and protonic H\u03b4+. These active hydrogens are responsible for the successive C-end and O-end activations of CO2 and hence the final product (HCOOH). This finding represents a good example of an indirect hydrogen source used in CO2 hydrogenation through reactivity tuned by silicon incorporation, and thus the underlying mechanism will be valuable for the design of similar reactions.<\/jats:p>","DOI":"10.3390\/molecules26010050","type":"journal-article","created":{"date-parts":[[2020,12,24]],"date-time":"2020-12-24T09:02:44Z","timestamp":1608800564000},"page":"50","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Hydrogenation of CO2 Promoted by Silicon-Activated H2S: Origin and Implications"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7285-2515","authenticated-orcid":false,"given":"Xing","family":"Liu","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,12,24]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1158","DOI":"10.1038\/nature08017","article-title":"Greenhouse-gas emission targets for limiting global warming to 2 \u00b0C","volume":"458","author":"Meinshausen","year":"2009","journal-title":"Nature"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1038\/s41586-018-0181-4","article-title":"The many possible climates from the Paris Agreement\u2019s aim of 1.5 \u00b0C warming","volume":"558","author":"Seneviratne","year":"2018","journal-title":"Nature"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3193","DOI":"10.1039\/C8CS00502H","article-title":"New horizon in C1 chemistry: Breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels","volume":"48","author":"Zhou","year":"2019","journal-title":"Chem. Soc. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4580","DOI":"10.1039\/C7CY01403A","article-title":"A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons","volume":"7","author":"Yang","year":"2017","journal-title":"Catal. Sci. Technol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1800","DOI":"10.1039\/C9GC04342J","article-title":"Catalytic transformation of CO2 into C1 chemicals using hydrosilanes as a reducing agent","volume":"22","author":"Zhang","year":"2020","journal-title":"Green Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"598","DOI":"10.2105\/AJPH.20.6.598","article-title":"Hydrogen sulphide in industry\u2014Occurrence, effects, and treatment","volume":"20","author":"Yant","year":"1930","journal-title":"Am. J. Public Health Nations Health"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1016\/j.apsusc.2017.06.295","article-title":"Illuminate the active sites of \u03b3-FeOOH for low-temperature desulfurization","volume":"425","author":"Shen","year":"2017","journal-title":"Appl. Surf. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1385","DOI":"10.1039\/C9CS00614A","article-title":"State of the art and perspectives in heterogeneous catalysis of CO2 hydrogenation to methanol","volume":"49","author":"Zhong","year":"2020","journal-title":"Chem. Soc. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"7930","DOI":"10.1021\/jacs.0c01855","article-title":"CO2 hydrogenation to formate and formic acid by bimetallic palladium-copper hydride clusters","volume":"142","author":"Liu","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"7984","DOI":"10.1021\/acs.chemrev.9b00723","article-title":"Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis","volume":"120","author":"Jiang","year":"2020","journal-title":"Chem. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"9331","DOI":"10.1021\/jp3051092","article-title":"Computational studies of CO2 activation via photochemical reactions with reduced sulfur compounds","volume":"116","author":"Baltrusaitis","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1056","DOI":"10.1039\/C8CC08075E","article-title":"Reduction of CO2 with H2S in a simulated deep-sea hydrothermal vent system","volume":"55","author":"He","year":"2019","journal-title":"Chem. Commun."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"10044","DOI":"10.1021\/acscatal.9b02986","article-title":"Inhibitor, co-catalyst, or co-reactant? Probing the different roles of H2S during CO2 hydrogenation on the MoS2 catalyst","volume":"9","author":"Upadhyay","year":"2019","journal-title":"ACS Catal."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4359","DOI":"10.1002\/chem.201504953","article-title":"Hydrogen sulfide induced carbon dioxide activation by metal-free dual catalysis","volume":"22","author":"Kumar","year":"2016","journal-title":"Chem. Eur. J."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1016\/S0920-5861(02)00309-7","article-title":"Catalytic synthesis of methanethiol from hydrogen sulfide and carbon monoxide over vanadium-based catalysts","volume":"78","author":"Mul","year":"2003","journal-title":"Catal. Today"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"264","DOI":"10.1016\/j.jcat.2011.03.027","article-title":"Synthesis of methyl mercaptan from carbonyl sulfide over sulfide K2MoO4\/SiO2","volume":"280","author":"Gutierrez","year":"2011","journal-title":"J. Catal."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1595","DOI":"10.1021\/cs200455k","article-title":"Synthesis of methanethiol from carbonyl sulfide and carbon disulfide on (Co)K-promoted sulfide Mo\/SiO2 catalysts","volume":"1","author":"Gutierrez","year":"2011","journal-title":"ACS Catal."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1016\/j.molcata.2007.12.014","article-title":"Direct synthesis of methanethiol from H2S-rich syngas over sulfided Mo-based catalysts","volume":"283","author":"Chen","year":"2008","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"471","DOI":"10.1039\/B312340P","article-title":"Catalytic synthesis of methanethiol from CO\/H2\/H2S mixtures using \u03b1-Al2O3","volume":"28","author":"Zhang","year":"2004","journal-title":"New J. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"7023","DOI":"10.1021\/acs.jpca.8b04428","article-title":"Splitting of hydrogen sulfide by group 14 elements (Si, Ge, Sn, Pb) in excess argon at cryogenic temperatures","volume":"122","author":"Liu","year":"2018","journal-title":"J. Phys. Chem. A"},{"key":"ref_21","first-page":"75","article-title":"High-temperature photoelectron spectroscopy. A study of SiS(X 1\u03a3+)","volume":"85","author":"Cockett","year":"1989","journal-title":"J. Chem. Soc. Faraday Trans. 2 Mol. Chem. Phys."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1579","DOI":"10.1039\/B618799D","article-title":"Rotational spectroscopy of the isotopic species of silicon monosulfide, SiS","volume":"9","author":"Muller","year":"2007","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4583","DOI":"10.1021\/ja00195a009","article-title":"Matrix IR spectrum and ab initio SCF calculations of molecular SiS2","volume":"111","author":"Schnockel","year":"1989","journal-title":"J. Am. Chem. Soc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"4826","DOI":"10.1021\/jacs.7b11267","article-title":"Determinant role of electrogenerated reactive nucleophilic species on selectivity during reduction of CO2 catalyzed by metalloporphyrins","volume":"140","author":"Gottle","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"9728","DOI":"10.1021\/jacs.7b05591","article-title":"Lattice-hydride mechanism in electrocatalytic CO2 reduction by structurally precise copper-hydride nanoclusters","volume":"139","author":"Tang","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"7323","DOI":"10.1002\/anie.201201282","article-title":"Deoxygenative reduction of carbon dioxide to methane, toluene, and diphenylmethane with [Et2Al]+ as catalyst","volume":"51","author":"Khandelwal","year":"2012","journal-title":"Angew. Int. Ed. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/ncomms12553","article-title":"Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals","volume":"7","author":"Sun","year":"2016","journal-title":"Nat. Commun."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3114","DOI":"10.1039\/C7CC00125H","article-title":"CO2 to methanol conversion using hydride terminated porous silicon nanoparticles","volume":"53","author":"Dasog","year":"2017","journal-title":"Chem. Commun."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1700118","DOI":"10.1002\/adsu.201700118","article-title":"Tailoring CO2 reduction with doped silicon nanocrystals","volume":"1","author":"Wong","year":"2017","journal-title":"Adv. Sustain. Syst."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"46","DOI":"10.1038\/s41929-018-0199-x","article-title":"Catalytic CO2 reduction by palladium-decorated silicon-hydride nanosheets","volume":"2","author":"Qian","year":"2019","journal-title":"Nat. Catal."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"8171","DOI":"10.1039\/c2ee21928j","article-title":"Formic acid as a hydrogen source\u2014recent developments and future trends","volume":"5","author":"Grasemann","year":"2012","journal-title":"Energy Environ. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"12127","DOI":"10.1021\/acs.jpcc.7b00278","article-title":"Why low valent lead (II) hydride complex would be a better catalyst for CO2 activation than its 14 group analogues?","volume":"121","author":"Ortega","year":"2017","journal-title":"J. Phys. Chem. C"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1062","DOI":"10.1021\/jz200215s","article-title":"From elements to clusters: The periodic table revisited","volume":"2","author":"Castleman","year":"2011","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1432","DOI":"10.1021\/jz400156t","article-title":"Beyond the periodic table of elements: The role of superatoms","volume":"4","author":"Jena","year":"2013","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"2931","DOI":"10.1021\/ar5001583","article-title":"Special and general superatoms","volume":"47","author":"Luo","year":"2014","journal-title":"Acc. Chem. Res."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"5755","DOI":"10.1021\/acs.chemrev.7b00524","article-title":"Super atomic clusters: Design rules and potential for building blocks of materials","volume":"118","author":"Jena","year":"2018","journal-title":"Chem. Rev."},{"key":"ref_37","unstructured":"Dean, J.A. (1999). Lange\u2019s Handbook of Chemistry, McGraw Hill. [15th ed.]."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2177","DOI":"10.1039\/C6EE00383D","article-title":"CO2 photo-reduction: Insights into CO2 activation and reaction on surfaces of photocatalysts","volume":"9","author":"Chang","year":"2016","journal-title":"Energy Environ. Sci."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2063","DOI":"10.1016\/j.cpc.2012.05.008","article-title":"CALYPSO: A method for crystal structure prediction","volume":"183","author":"Wang","year":"2012","journal-title":"Comput. Phys. Commun."},{"key":"ref_40","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Gaussian 09 Revision d 01, Gaussian Inc."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B Condens. Matter Mater. Phys."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"3265","DOI":"10.1063\/1.447079","article-title":"Self-consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets","volume":"80","author":"Frisch","year":"1984","journal-title":"J. Chem. Phys."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"084104","DOI":"10.1063\/1.4746757","article-title":"Particle-swarm structure prediction on clusters","volume":"137","author":"Lv","year":"2012","journal-title":"J. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"6796","DOI":"10.1063\/1.462569","article-title":"Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functions","volume":"96","author":"Kendall","year":"1992","journal-title":"J. Chem. Phys."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1358","DOI":"10.1063\/1.464303","article-title":"Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon","volume":"98","author":"Woon","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"11099","DOI":"10.1063\/1.1622923","article-title":"Systematically convergent basis sets with relativistic pseudopotentials. I. Correlation consistent basis sets for the post-d group 13\u201315 elements","volume":"119","author":"Peterson","year":"2003","journal-title":"J. Chem. Phys."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"13683","DOI":"10.1039\/c1cp20834a","article-title":"Validation of electronic structure methods for isomerization reactions of large organic molecules","volume":"13","author":"Luo","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"4025","DOI":"10.1021\/acs.jpca.6b02600","article-title":"Benchmark calculations for bond dissociation enthalpies of unsaturated methyl esters and the bond dissociation enthalpies of methyl linolenate","volume":"120","author":"Li","year":"2016","journal-title":"J. Phys. Chem. A"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1021\/ct0499783","article-title":"Using Hessian updating to increase the efficiency of a Hessian based predictor-corrector reaction path following method","volume":"1","author":"Hratchian","year":"2005","journal-title":"J. Chem. Theory Comput."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1103\/RevModPhys.79.291","article-title":"Coupled-cluster theory in quantum chemistry","volume":"79","author":"Bartlett","year":"2007","journal-title":"Rev. Mod. Phys."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"4049","DOI":"10.1021\/ja00326a036","article-title":"Density functional approach to the frontier-electron theory of chemical reactivity","volume":"106","author":"Parr","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"205","DOI":"10.1021\/jp046577a","article-title":"New dual descriptor for chemical reactivity","volume":"109","author":"Morell","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_55","doi-asserted-by":"crossref","unstructured":"Chattaraj, P.K. (2009). Chemical reactivity concepts in density functional theory. Chemical Reactivity Theory\u2014A Density Functional View, CRC Press.","DOI":"10.1201\/9781420065442"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"1793","DOI":"10.1021\/cr990029p","article-title":"Conceptual density functional theory","volume":"103","author":"Geerlings","year":"2003","journal-title":"Chem. Rev."},{"key":"ref_57","unstructured":"Dennington, R., Keith, T., and Millam, J. (2009). Gauss View, Semichem Inc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/1\/50\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T10:45:40Z","timestamp":1760179540000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/1\/50"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,12,24]]},"references-count":57,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2021,1]]}},"alternative-id":["molecules26010050"],"URL":"https:\/\/doi.org\/10.3390\/molecules26010050","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,12,24]]}}}