{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T13:24:33Z","timestamp":1787232273990,"version":"build-2736575974"},"reference-count":27,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T00:00:00Z","timestamp":1785974400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006151","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-SC0021266"],"award-info":[{"award-number":["DE-SC0021266"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004281","name":"Narodowe Centrum Nauki","doi-asserted-by":"publisher","award":["UMO-2023\/50\/E\/ST4\/00197"],"award-info":[{"award-number":["UMO-2023\/50\/E\/ST4\/00197"]}],"id":[{"id":"10.13039\/501100004281","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006445","name":"Uniwersytet Warszawski","doi-asserted-by":"publisher","award":["G83-28"],"award-info":[{"award-number":["G83-28"]}],"id":[{"id":"10.13039\/501100006445","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006445","name":"Uniwersytet Warszawski","doi-asserted-by":"publisher","award":["GB80-24"],"award-info":[{"award-number":["GB80-24"]}],"id":[{"id":"10.13039\/501100006445","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,20]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Rising CO2 emissions in the atmosphere continue to be among the world\u2019s most preeminent environmental challenges. Indeed, the solution of carbon sequestration via geologic storage has proved insufficient to combat this problem. The alternative to sequestration is the electrochemical reduction of carbon dioxide to liquid products, a common step to combat net warming effects. However, the electrochemical reduction of carbon dioxide remains limited because of several competing pathways and potential-dependent kinetics at catalytic surfaces. Herein, we consider Cu-phthalocyanine Metal\u2013Organic Framework (MOF) as a candidate electrocatalyst to reduce CO2 to a single hydrocarbon product. To achieve this, we develop a first-principles Grand Canonical Potential Kinetics (GCP-K) framework for quantifying the activity and product selectivity of said MOF catalyst. Our model is derived directly from constant-potential DFT calculations, from which reaction free energies and activation barriers are extracted across the relevant electrochemical manifold. Potential dependence is incorporated through explicit charge-transfer symmetry factors, enabling the systematic construction of potential-resolved rate constants. On this basis, we assemble a microkinetic reaction network that encompasses the competing pathways leading to C1 and C2 liquid products. We calculate Faradaic efficiency maps across multiple selectivity windows from branch points in different microenvironments. We find that charge-transfer processes shift the adsorption energy of any individual intermediate by only a few millivolts per 0.1 V of applied bias, but the cumulative effect across multistep PCET sequences displaces the selectivity windows by tens to hundreds of millivolts. We calculate selectivity-limiting steps and the various kinetic rates associated with them as a function of potential and surface coverage. In addition to mechanistic investigations of each reaction framework in question, we elucidate the stabilization of various oxygenated intermediates and their role in creating different C1 and C2 products. Taken as a whole, these results show a variety of catalyst-level design levers that could increase the liquid product window and offer a mechanistic foundation for selecting the operating potentials that maximize desired product selectivity at functional current densities.<\/jats:p>","DOI":"10.1021\/acs.jpcc.6c03863","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T14:03:38Z","timestamp":1786025018000},"page":"11634-11644","source":"Crossref","is-referenced-by-count":0,"title":["Competition between\nGas and Liquid Solar Fuel Product\nFormation from the CO2 Reduction Reaction on Two-Dimensional\nMetal-Organic Framework"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0974-5968","authenticated-orcid":true,"given":"Aarya D.","family":"Riasati","sequence":"first","affiliation":[{"name":"California Institute of Technology , , MC 139-74 , , ,","place":["Pasadena, California, United States, 91125"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0097-5716","authenticated-orcid":true,"suffix":"III","given":"William A.","family":"Goddard","sequence":"additional","affiliation":[{"name":"California Institute of Technology , , MC 139-74 , , ,","place":["Pasadena, California, United States, 91125"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8541-1914","authenticated-orcid":true,"given":"Silvio","family":"Osella","sequence":"additional","affiliation":[{"name":"California Institute of Technology , , MC 139-74 , , ,","place":["Pasadena, California, United States, 91125"]},{"name":"University of Warsaw , , Banacha 2C , ,","place":["Warsaw, Poland, 02-097"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,6]]},"reference":[{"key":"2026082008280057800_cit1","doi-asserted-by":"publisher","first-page":"115762","DOI":"10.1016\/j.rser.2025.115762","article-title":"Strategies for Achieving Carbon Neutrality within the\nChemical Industry","volume":"217","author":"Malehmirchegini","year":"2025","journal-title":"Renewable Sustainable Energy\nRev."},{"issue":"8","key":"2026082008280057800_cit2","doi-asserted-by":"publisher","first-page":"1700","DOI":"10.1016\/j.joule.2023.07.010","article-title":"Molecular Tuning for\nElectrochemical\nCO2 Reduction","volume":"7","author":"Zhang","year":"2023","journal-title":"Joule"},{"issue":"8","key":"2026082008280057800_cit3","doi-asserted-by":"publisher","first-page":"3504","DOI":"10.3390\/molecules28083504","article-title":"Cutting-Edge\nElectrocatalysts for\nCO2RR","volume":"28","author":"Jeyachandran","year":"2023","journal-title":"Molecules"},{"key":"2026082008280057800_cit4","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202502425","article-title":"Two-Dimensional Conjugated\nMetal\u2013Organic Frameworks as Electrocatalysts\nfor Boosting Glycerol Upgrading Coupled with Hydrogen Production","volume":"64","author":"Luo","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"issue":"8","key":"2026082008280057800_cit5","doi-asserted-by":"publisher","first-page":"4602","DOI":"10.1021\/acs.chemrev.2c00667","article-title":"Porous Organic Cages","volume":"123","author":"Yang","year":"2023","journal-title":"Chem. Rev."},{"key":"2026082008280057800_cit6","doi-asserted-by":"publisher","first-page":"1759","DOI":"10.1021\/acsnano.1c10544","article-title":"Two-Dimensional\nConjugated Metal\u2013Organic Frameworks for Electrocatalysis: Opportunities\nand Challenges","volume":"16","author":"Zhong","year":"2022","journal-title":"ACS Nano"},{"key":"2026082008280057800_cit7","doi-asserted-by":"publisher","first-page":"1208","DOI":"10.1126\/science.aac8343","article-title":"Covalent Organic\nFrameworks Comprising Cobalt Porphyrins for Catalytic CO2 Reduction in Water","volume":"349","author":"Lin","year":"2015","journal-title":"Science"},{"key":"2026082008280057800_cit8","doi-asserted-by":"publisher","first-page":"13624","DOI":"10.1021\/jacs.1c05051","article-title":"Interfacial Synthesis\nof Layer-Oriented 2D Conjugated Metal\u2013Organic Framework Films\ntoward Directional Charge Transport","volume":"143","author":"Wang","year":"2021","journal-title":"J. Am.\nChem. Soc."},{"key":"2026082008280057800_cit9","unstructured":"MarketsandMarkets.\n          \n          Global Methanol Market, Industry\nSize Forecast; MarketsandMarkets, 2025. https:\/\/www.marketsandmarkets.com\/Market-Reports\/methanol-market-425.html. (Accessed 2025\u201310\u201316)."},{"key":"2026082008280057800_cit10","unstructured":"MarketsandMarkets.\n          \n          Ethanol Market \u2013 Global\nTrends and Forecasts to 2018; MarketsandMarkets, 2025. https:\/\/www.marketsandmarkets.com\/Market-Reports\/biofuels-market-297.html. (Accessed 2025\u201310\u201316)."},{"issue":"6","key":"2026082008280057800_cit11","doi-asserted-by":"publisher","first-page":"1698","DOI":"10.3390\/su10061698","article-title":"Assessing the Contribution\nof Bioeconomy to the Total Economy: A Review of National Frameworks","volume":"10","author":"Bracco","year":"2018","journal-title":"Sustainability"},{"issue":"39","key":"2026082008280057800_cit12","doi-asserted-by":"publisher","first-page":"21319","DOI":"10.1021\/jacs.3c05650","article-title":"CO2 Reduction to Methane\nand Ethylene on a Single-Atom Catalyst: A Grand Canonical Quantum\nMechanics Study","volume":"145","author":"Osella","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026082008280057800_cit13","doi-asserted-by":"publisher","first-page":"041706","DOI":"10.1063\/1.5047829","article-title":"Grand-Canonical Approach\nto Density Functional Theory of Electrocatalytic Systems: Thermodynamics\nof Solid\u2013Liquid Interfaces at Constant Ion and Electrode Potentials","volume":"150","author":"Melander","year":"2019","journal-title":"J. Chem. Phys."},{"key":"2026082008280057800_cit14","doi-asserted-by":"publisher","first-page":"17953","DOI":"10.1103\/PhysRevB.50.17953","article-title":"Projector\nAugmented-Wave Method","volume":"50","author":"Blo\u0308chl","year":"1994","journal-title":"Phys. Rev. B"},{"key":"2026082008280057800_cit15","doi-asserted-by":"publisher","first-page":"11169","DOI":"10.1103\/PhysRevB.54.11169","article-title":"Efficient\nIterative Schemes for Ab Initio Total-Energy\nCalculations Using a Plane-Wave Basis Set","volume":"54","author":"Kresse","year":"1996","journal-title":"Phys.\nRev. B"},{"key":"2026082008280057800_cit16","doi-asserted-by":"publisher","first-page":"15","DOI":"10.1016\/0927-0256(96)00008-0","article-title":"Efficiency\nof Ab-Initio Total Energy Calculations for\nMetals and Semiconductors Using a Plane-Wave Basis Set","volume":"6","author":"Kresse","year":"1996","journal-title":"Comput. Mater. Sci."},{"key":"2026082008280057800_cit17","doi-asserted-by":"publisher","first-page":"234101","DOI":"10.1063\/1.5132354","article-title":"Implicit Self-Consistent Electrolyte Model in Plane-Wave\nDensity-Functional Theory","volume":"151","author":"Mathew","year":"2019","journal-title":"J. Chem. Phys."},{"key":"2026082008280057800_cit18","doi-asserted-by":"publisher","first-page":"084106","DOI":"10.1063\/1.4865107","article-title":"Implicit\nSolvation Model for Density-Functional Study of Nanocrystal Surfaces\nand Reaction Pathways","volume":"140","author":"Mathew","year":"2014","journal-title":"J. Chem. 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Faraday Soc."},{"key":"2026082008280057800_cit25","doi-asserted-by":"publisher","first-page":"2005","DOI":"10.1021\/cr9001808","article-title":"Reactivity Theory\nof Transition-Metal Surfaces: A Br\u00f8nsted\u2013Evans\u2013Polanyi\nLinear Activation Energy\u2013Free-Energy Analysis","volume":"110","author":"van Santen","year":"2010","journal-title":"Chem. Rev."},{"key":"2026082008280057800_cit26","doi-asserted-by":"publisher","first-page":"82","DOI":"10.1016\/j.cattod.2018.03.048","article-title":"Using Br\u00f8nsted-Evans-Polanyi\nRelations to Predict Electrode Potential Dependent Activation Energies","volume":"312","author":"Akhade","year":"2018","journal-title":"Catal. Today"},{"key":"2026082008280057800_cit27","doi-asserted-by":"publisher","first-page":"909","DOI":"10.1038\/nmat1752","article-title":"Computational high-throughput screening of electrocatalytic\nmaterials for hydrogen evolution","volume":"5","author":"Greeley","year":"2006","journal-title":"Nat. Mater."}],"container-title":["The Journal of Physical\nChemistry C"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcc.6c03863","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpccck\/article-pdf\/130\/33\/11634\/66442082\/acs.jpcc.6c03863.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpccck\/article-pdf\/130\/33\/11634\/66442082\/acs.jpcc.6c03863.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T12:29:52Z","timestamp":1787228992000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpccck\/article\/130\/33\/11634\/5249082\/Competition-between-Gas-and-Liquid-Solar-Fuel"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,6]]},"references-count":27,"journal-issue":{"issue":"33","published-online":{"date-parts":[[2026,8,6]]},"published-print":{"date-parts":[[2026,8,20]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcc.6c03863","relation":{},"ISSN":["1932-7447","1932-7455"],"issn-type":[{"value":"1932-7447","type":"print"},{"value":"1932-7455","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,6]]}}}