{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T13:11:35Z","timestamp":1790255495168,"version":"4.1.0"},"reference-count":41,"publisher":"American Chemical Society (ACS)","issue":"38","license":[{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["2025YFE0107600"],"award-info":[{"award-number":["2025YFE0107600"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100019092","name":"Science Fund for Distinguished Young Scholars of Hunan Province","doi-asserted-by":"publisher","award":["2025JJ20019"],"award-info":[{"award-number":["2025JJ20019"]}],"id":[{"id":"10.13039\/501100019092","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Molecular catalyst\/semiconductor photocathodes require coordinated regulation of interfacial energetics and catalytic-site electronic structure for efficient solar CO2 reduction. Here, we show that peripheral substituent engineering in nickel phthalocyanines integrated on p-Si nanowires provides a molecular strategy to couple the interfacial response of p-Si\/NiPc-X photocathodes with Ni\u2013N4-centered CO2 activation. Frequency-dependent Mott-Schottky responses show a clearly resolved positive apparent interfacial capacitance-transition potential for NiPc-NH2\/Si, while UPS and light\/dark OCP measurements indicate an amino-substitution-associated interfacial electronic response. EIS and IMPS further reveal lower charge-transfer resistance and 92.7% charge-transfer efficiency for NiPc-NH2\/Si, indicating improved photocarrier utilization. In parallel, Ni 2p XPS and Hirshfeld charge analysis indicate electron enrichment at the Ni\u2013N4 center, and DFT calculations show that the thermodynamic free-energy requirement for *COOH formation decreases from 2.03 to 1.75 eV. These coupled interfacial and catalytic-site effects enable NiPc-NH2\/Si to deliver 92.1% CO Faradaic efficiency and 2.8% applied-bias photon-to-current efficiency for solar CO2-to-CO conversion.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02212","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T15:01:53Z","timestamp":1789484513000},"page":"10966-10972","source":"Crossref","is-referenced-by-count":0,"title":["Substituent\nEngineering Couples Photocathode Interfacial\nEnergetics with Ni\u2013N4 Electronic Structure for Solar\nCO2 Reduction"],"prefix":"10.1021","volume":"17","author":[{"given":"Mulin","family":"Wu","sequence":"first","affiliation":[{"name":"Central South University , , ,","place":["Changsha, China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingyue","family":"Zou","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Keke","family":"Wang","sequence":"additional","affiliation":[{"name":"Hunan University of Science and Technology , , ,","place":["Xiangtan, China, 411201"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kewei","family":"Wu","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9007-4817","authenticated-orcid":true,"given":"Min","family":"Liu","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6801-4105","authenticated-orcid":true,"given":"Wenzhang","family":"Li","sequence":"additional","affiliation":[{"name":"Central South University , , ,","place":["Changsha, China, 410083"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,15]]},"reference":[{"issue":"5","key":"2026092408414688400_cit1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202213067","article-title":"Bias-Free Solar-Driven\nSyngas Production: A Fe2O3 Photoanode Featuring\nSingle-Atom Cobalt Integrated with a Silver-Palladium Cathode","volume":"62","author":"Zhao","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"issue":"31","key":"2026092408414688400_cit2","doi-asserted-by":"publisher","first-page":"1804710","DOI":"10.1002\/adma.201804710","article-title":"The Development\nof Cocatalysts for Photoelectrochemical CO2 Reduction","volume":"31","author":"Chang","year":"2019","journal-title":"Adv. Mater."},{"issue":"1","key":"2026092408414688400_cit3","doi-asserted-by":"publisher","first-page":"7111","DOI":"10.1038\/s41467-022-34926-x","article-title":"Back-Illuminated\nPhotoelectrochemical Flow Cell for Efficient CO2 Reduction","volume":"13","author":"Liu","year":"2022","journal-title":"Nat. Commun."},{"key":"2026092408414688400_cit4","doi-asserted-by":"publisher","first-page":"749","DOI":"10.1016\/j.jechem.2025.04.078","article-title":"Quasi-Diatomic\nSite-Tailored Molecular Catalyst on Si Nanowire Boosting Photoelectrocatalytic\nCO2 Reduction Efficiency at Ultralow Potential","volume":"108","author":"Wang","year":"2025","journal-title":"J. Energy Chem."},{"issue":"42","key":"2026092408414688400_cit5","doi-asserted-by":"publisher","first-page":"14152","DOI":"10.1021\/jacs.6b09212","article-title":"Photoelectrochemical\nReduction of CO2 Coupled to Water Oxidation Using a Photocathode\nwith a Ru(II)-Re(I) Complex Photocatalyst and a CoOx\/TaON\nPhotoanode","volume":"138","author":"Sahara","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"10","key":"2026092408414688400_cit6","doi-asserted-by":"publisher","first-page":"6138","DOI":"10.1021\/acscatal.5b01546","article-title":"Selective Catalytic\nElectroreduction of CO2 at Silicon Nanowires (SiNWs) Photocathodes\nUsing Non-Noble Metal-Based Manganese Carbonyl Bipyridyl Molecular\nCatalysts in Solution and Grafted onto SiNWs","volume":"5","author":"Torralba-Pen\u0303alver","year":"2015","journal-title":"ACS Catal."},{"issue":"4","key":"2026092408414688400_cit7","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202215213","article-title":"Aqueous Photoelectrochemical\nCO2 Reduction to CO and Methanol over a Silicon Photocathode\nFunctionalized with a Cobalt Phthalocyanine Molecular Catalyst","volume":"62","author":"Shang","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"issue":"7","key":"2026092408414688400_cit8","doi-asserted-by":"publisher","first-page":"2265","DOI":"10.1021\/acsenergylett.2c01147","article-title":"Monolayer Molecular\nFunctionalization Enabled by Acid-Base Interaction for High-Performance\nPhotochemical CO2 Reduction","volume":"7","author":"Shang","year":"2022","journal-title":"ACS\nEnergy Lett."},{"issue":"12","key":"2026092408414688400_cit9","doi-asserted-by":"publisher","first-page":"7998","DOI":"10.1021\/jacs.3c10837","article-title":"Photoelectrochemical\nCO2 Reduction to CO Enabled by a Molecular Catalyst Attached\nto High-Surface-Area Porous Silicon","volume":"146","author":"Jia","year":"2024","journal-title":"J. Am.\nChem. Soc."},{"issue":"3","key":"2026092408414688400_cit10","doi-asserted-by":"publisher","first-page":"569","DOI":"10.1021\/acsmaterialsau.5c00010","article-title":"Design Strategies for Coupling CO2 Reduction\nMolecular Electrocatalysts to Silicon Photocathodes","volume":"5","author":"Saund","year":"2025","journal-title":"ACS Mater. Au"},{"issue":"4","key":"2026092408414688400_cit11","doi-asserted-by":"publisher","first-page":"998","DOI":"10.1039\/D3QI02293E","article-title":"Tailoring Co-Catalysts on Si Photocathodes\nfor Efficient Photoelectrochemical CO2 Reduction: Recent\nProgress and Prospects of Deposition Methods","volume":"11","author":"Seo","year":"2024","journal-title":"Inorg. Chem. Front."},{"issue":"7","key":"2026092408414688400_cit12","doi-asserted-by":"publisher","first-page":"102462","DOI":"10.1016\/j.chempr.2025.102462","article-title":"Photoelectrocatalytic\nReduction of CO2 to Formate Using Immobilized Molecular\nManganese Catalysts on Oxidized Porous Silicon","volume":"11","author":"Hong","year":"2025","journal-title":"Chem."},{"issue":"9","key":"2026092408414688400_cit13","doi-asserted-by":"publisher","first-page":"4631","DOI":"10.1021\/acs.chemrev.7b00459","article-title":"Homogeneously Catalyzed Electroreduction\nof Carbon Dioxide-Methods, Mechanisms, and Catalysts","volume":"118","author":"Francke","year":"2018","journal-title":"Chem. Rev."},{"issue":"6","key":"2026092408414688400_cit14","doi-asserted-by":"publisher","first-page":"2423","DOI":"10.1039\/C2CS35360A","article-title":"Catalysis\nof the Electrochemical\nReduction of Carbon Dioxide","volume":"42","author":"Costentin","year":"2013","journal-title":"Chem. Soc. Rev."},{"issue":"10","key":"2026092408414688400_cit15","doi-asserted-by":"publisher","first-page":"775","DOI":"10.1038\/s41929-020-00512-x","article-title":"Towards Molecular\nUnderstanding of\nLocal Chemical Environment Effects in Electro- and Photocatalytic\nCO2 Reduction","volume":"3","author":"Wagner","year":"2020","journal-title":"Nat. Catal."},{"issue":"3","key":"2026092408414688400_cit16","doi-asserted-by":"publisher","first-page":"2267","DOI":"10.1021\/jacs.3c13540","article-title":"Tailoring\nInterfaces for Enhanced Methanol Production from Photoelectrochemical\nCO2 Reduction","volume":"146","author":"Shang","year":"2024","journal-title":"J. Am. Chem. Soc."},{"issue":"7784","key":"2026092408414688400_cit17","doi-asserted-by":"publisher","first-page":"639","DOI":"10.1038\/s41586-019-1760-8","article-title":"Domino Electroreduction\nof CO2 to Methanol on a Molecular Catalyst","volume":"575","author":"Wu","year":"2019","journal-title":"Nature"},{"issue":"9","key":"2026092408414688400_cit18","doi-asserted-by":"publisher","first-page":"684","DOI":"10.1038\/s41560-020-0667-9","article-title":"Molecular\nEngineering of Dispersed Nickel Phthalocyanines on Carbon\nNanotubes for Selective CO2 Reduction","volume":"5","author":"Zhang","year":"2020","journal-title":"Nat. Energy"},{"issue":"16","key":"2026092408414688400_cit19","doi-asserted-by":"publisher","first-page":"3149","DOI":"10.1021\/acs.accounts.1c00200","article-title":"Heterogeneous Molecular Catalysts\nof Metal Phthalocyanines for Electrochemical CO2 Reduction\nReactions","volume":"54","author":"Wu","year":"2021","journal-title":"Acc. Chem. Res."},{"issue":"10","key":"2026092408414688400_cit20","doi-asserted-by":"publisher","first-page":"2111322","DOI":"10.1002\/adfm.202111322","article-title":"Ligand Engineering\nin Nickel Phthalocyanine\nto Boost the Electrocatalytic Reduction of CO2","volume":"32","author":"Chen","year":"2022","journal-title":"Adv. Funct. Mater."},{"issue":"17","key":"2026092408414688400_cit21","doi-asserted-by":"publisher","first-page":"4705","DOI":"10.1021\/acs.jpclett.4c00774","article-title":"Insight into\nImpacts of \u03c0-\u03c0 Assembly on Phthalocyanine Based Heterogeneous\nMolecular Electrocatalysis","volume":"15","author":"Yang","year":"2024","journal-title":"J. Phys. Chem. Lett."},{"issue":"1","key":"2026092408414688400_cit22","doi-asserted-by":"publisher","first-page":"66","DOI":"10.1021\/acsaem.8b01563","article-title":"Decoupling\nEffects of Surface Recombination and Barrier Height on p-Si(111) Photovoltage\nin Semiconductor|Liquid Junctions via Molecular Dipoles and Metal\nOxides","volume":"2","author":"Boucher","year":"2019","journal-title":"ACS Appl. Energy Mater."},{"issue":"6","key":"2026092408414688400_cit23","doi-asserted-by":"publisher","first-page":"2567","DOI":"10.1021\/jacs.0c12075","article-title":"Tuning p-Si(111)\nPhotovoltage via Molecule|Semiconductor Electronic Coupling","volume":"143","author":"Boucher","year":"2021","journal-title":"J. Am. Chem. Soc."},{"issue":"12","key":"2026092408414688400_cit24","doi-asserted-by":"publisher","first-page":"5657","DOI":"10.1021\/jacs.9b12824","article-title":"Non-Catalytic Benefits\nof Ni(II) Binding to an Si(111)-PNP\nConstruct for Photoelectrochemical Hydrogen Evolution Reaction: Metal\nIon Induced Flat Band Potential Modulation","volume":"142","author":"Gurrentz","year":"2020","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026092408414688400_cit25","doi-asserted-by":"publisher","first-page":"1901","DOI":"10.1039\/C9EE00748B","article-title":"Stable\nand Tunable Phosphonic Acid Dipole Layer\nfor Band Edge Engineering of Photoelectrochemical and Photovoltaic\nHeterojunction Devices","volume":"12","author":"Wick-Joliat","year":"2019","journal-title":"Energy Environ. Sci."},{"issue":"4","key":"2026092408414688400_cit26","doi-asserted-by":"publisher","first-page":"1777","DOI":"10.1021\/acsenergylett.4c00122","article-title":"Methyl\nTermination of p-Type Silicon\nEnables Selective Photoelectrochemical CO2 Reduction by\na Molecular Ruthenium Catalyst","volume":"9","author":"Bein","year":"2024","journal-title":"ACS Energy Lett."},{"issue":"27","key":"2026092408414688400_cit27","doi-asserted-by":"publisher","first-page":"6301","DOI":"10.1021\/acs.jpclett.3c00672","article-title":"Modulating the Cu2O Photoelectrode\/Electrolyte\nInterface with Bilayer Surfactant Simulating Cell Membranes for Boosting\nPhotoelectrochemical CO2 Reduction","volume":"14","author":"Zhang","year":"2023","journal-title":"J. Phys. Chem. Lett."},{"issue":"7","key":"2026092408414688400_cit28","doi-asserted-by":"publisher","first-page":"2549","DOI":"10.1021\/acsenergylett.1c01245","article-title":"Mott-Schottky\nAnalysis of Photoelectrodes: Sanity Checks Are Needed","volume":"6","author":"Sivula","year":"2021","journal-title":"ACS Energy Lett."},{"issue":"45","key":"2026092408414688400_cit29","doi-asserted-by":"publisher","first-page":"26162","DOI":"10.1039\/C9TA09569A","article-title":"Flat Band\nPotential Determination: Avoiding the Pitfalls","volume":"7","author":"Hankin","year":"2019","journal-title":"J. Mater. Chem. A"},{"issue":"38","key":"2026092408414688400_cit30","doi-asserted-by":"publisher","first-page":"13466","DOI":"10.1021\/acs.langmuir.3c01158","article-title":"Photoelectrochemical\nMethods for the Determination of the Flat-Band Potential in Semiconducting\nPhotocatalysts: A Comparison Study","volume":"39","author":"Koshevoy","year":"2023","journal-title":"Langmuir"},{"issue":"4","key":"2026092408414688400_cit31","doi-asserted-by":"publisher","first-page":"685","DOI":"10.1021\/ed084p685","article-title":"Flat-Band Potential of a Semiconductor: Using the Mott-Schottky\nEquation","volume":"84","author":"Gelderman","year":"2007","journal-title":"J. Chem. Educ."},{"issue":"1","key":"2026092408414688400_cit32","doi-asserted-by":"publisher","first-page":"606","DOI":"10.1021\/acscatal.6b02382","article-title":"Probing the Reaction\nMechanism of CO2 Electroreduction\nover Ag Films via Operando Infrared Spectroscopy","volume":"7","author":"Firet","year":"2017","journal-title":"ACS Catal."},{"issue":"3","key":"2026092408414688400_cit33","doi-asserted-by":"publisher","first-page":"682","DOI":"10.1021\/acsenergylett.8b02525","article-title":"CO2 Electrochemical\nReduction\nAs Probed through Infrared Spectroscopy","volume":"4","author":"Zhu","year":"2019","journal-title":"ACS\nEnergy Lett."},{"issue":"44","key":"2026092408414688400_cit34","doi-asserted-by":"publisher","first-page":"15664","DOI":"10.1021\/jacs.7b10462","article-title":"Direct Observation\non Reaction Intermediates and the Role of Bicarbonate Anions in CO2 Electrochemical Reduction Reaction on Cu Surfaces","volume":"139","author":"Zhu","year":"2017","journal-title":"J. Am. Chem. Soc."},{"issue":"15","key":"2026092408414688400_cit35","doi-asserted-by":"publisher","first-page":"8049","DOI":"10.1021\/acscatal.0c02130","article-title":"Infrared Analysis of\nInterfacial Phenomena during Electrochemical\nReduction of CO2 over Polycrystalline Copper Electrodes","volume":"10","author":"Moradzaman","year":"2020","journal-title":"ACS Catal."},{"key":"2026092408414688400_cit36","doi-asserted-by":"publisher","first-page":"109728","DOI":"10.1016\/j.nanoen.2024.109728","article-title":"Understanding\nthe First Activation\nStep of Electrochemical CO2 Reduction over Ag and Ni-N-C\nActive Sites","volume":"127","author":"Wang","year":"2024","journal-title":"Nano Energy"},{"issue":"2","key":"2026092408414688400_cit37","doi-asserted-by":"publisher","first-page":"268","DOI":"10.1039\/D4EY00274A","article-title":"Neighboring Effects\nof Single-Atom Cobalt Enable High-Performance CO2 Photoreduction","volume":"3","author":"Yan","year":"2025","journal-title":"EES Catal."},{"issue":"20","key":"2026092408414688400_cit38","doi-asserted-by":"publisher","first-page":"4073","DOI":"10.1021\/acs.jpclett.5b01559","article-title":"Catalysts and Reaction Pathways for the Electrochemical\nReduction of Carbon Dioxide","volume":"6","author":"Kortlever","year":"2015","journal-title":"J. Phys. Chem.\nLett."},{"issue":"12","key":"2026092408414688400_cit39","doi-asserted-by":"publisher","first-page":"9575","DOI":"10.1021\/acscatal.3c05089","article-title":"Potential Dependence and Substituent Effect in CO2 Electroreduction on a Cobalt Phthalocyanine Catalyst","volume":"14","author":"Li","year":"2024","journal-title":"ACS Catal."},{"issue":"24","key":"2026092408414688400_cit40","doi-asserted-by":"publisher","first-page":"11496","DOI":"10.1039\/D4NR01269K","article-title":"Recent Progress on\nNickel Phthalocyanine-Based\nElectrocatalysts for CO2 Reduction","volume":"16","author":"Wu","year":"2024","journal-title":"Nanoscale"},{"issue":"24","key":"2026092408414688400_cit41","doi-asserted-by":"publisher","first-page":"8746","DOI":"10.1021\/ja503541v","article-title":"Ultrafast Charge\nTransfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced\nKerr Effect Spectroscopy","volume":"136","author":"Balakrishnan","year":"2014","journal-title":"J. Am. Chem. Soc."}],"container-title":["The Journal of Physical\nChemistry Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpclett.6c02212","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/38\/10966\/68514989\/acs.jpclett.6c02212.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/38\/10966\/68514989\/acs.jpclett.6c02212.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T12:54:33Z","timestamp":1790254473000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article\/17\/38\/10966\/5430227\/Substituent-Engineering-Couples-Photocathode"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,15]]},"references-count":41,"journal-issue":{"issue":"38","published-online":{"date-parts":[[2026,9,15]]},"published-print":{"date-parts":[[2026,9,24]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpclett.6c02212","relation":{},"ISSN":["1948-7185"],"issn-type":[{"value":"1948-7185","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,15]]}}}