{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,16]],"date-time":"2026-03-16T20:49:19Z","timestamp":1773694159985,"version":"3.50.1"},"reference-count":48,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2021,11,12]],"date-time":"2021-11-12T00:00:00Z","timestamp":1636675200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>Interest in cost-effective materials pushes researchers to the inexpensive and abundant semiconductors to use photons\u2019 energy for generating electrons and holes required for photocatalytic transformations. At the same time, polysilicon is one of the economic semiconductors with a disadvantage of high bandgap which could be solved by carbon-doping. We employed this strategy to the synthesis of carbon-doped polysilicon by a new approach starting from citric acid and methyltrimethoxysilane. The nanocomposite obtained was utterly characterized, and compared with bare polysilicon; increased UV\u2013Vis absorbance and shift to higher wavelengths were the most notable characteristics of the synthesized catalyst. The carbon-doped polysilicon was modified with Pd nanoparticles to obtain a new heterogeneous photocatalyst for the formic acid degradation. The decomposition of formic acid was photocatalyzed by the obtained nanocomposite with a hydrogen production turnover frequency of up to 690 h\u22121. Moreover, it was demonstrated that the catalyst is stable and recyclable.<\/jats:p>","DOI":"10.3390\/polym13223919","type":"journal-article","created":{"date-parts":[[2021,11,14]],"date-time":"2021-11-14T20:51:53Z","timestamp":1636923113000},"page":"3919","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Carbon-Doping as Efficient Strategy for Improving Photocatalytic Activity of Polysilicon Supported Pd in Hydrogen Evolution from Formic Acid"],"prefix":"10.3390","volume":"13","author":[{"given":"Amal","family":"Al-Azmi","sequence":"first","affiliation":[{"name":"Chemistry Department, Kuwait University, P.O. Box 5969, Safat 13060, Kuwait"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7306-6455","authenticated-orcid":false,"given":"Sajjad","family":"Keshipour","sequence":"additional","affiliation":[{"name":"Department of Nanotechnology, Faculty of Science, Urmia University, P.O. Box 165, Urmia 5756151818, Iran"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,11,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"694","DOI":"10.1016\/j.rser.2017.05.140","article-title":"Green fuel as alternative fuel for diesel engine: A review","volume":"80","author":"Othman","year":"2017","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"835","DOI":"10.1016\/j.jclepro.2019.02.046","article-title":"Review and evaluation of hydrogen production options for better environment","volume":"218","author":"Acar","year":"2019","journal-title":"J. Clean. Prod."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Cardoso, J.A.S.B., \u0160ljuki\u0107, B., Erdem, M., Sequeira, C.A.C., and Santos, D.M.F. (2018). Vine Shoots and Grape Stalks as Carbon Sources for Hydrogen Evolution Reaction Electrocatalyst Supports. Catalysts, 8.","DOI":"10.3390\/catal8020050"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"8098","DOI":"10.1021\/acsaem.9b01579","article-title":"Highly Efficient and Sustained Electrochemical Hydrogen Evolution by Embedded Pd-Nanoparticles on a Coordination Polymer\u2014Reduced Graphene Oxide Composite","volume":"2","author":"Alex","year":"2019","journal-title":"ACS Appl. Energy Mater."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"12721","DOI":"10.1039\/c3ta12531a","article-title":"Au@Pd core\u2013shell nanoclusters growing on nitrogen-doped mildly reduced graphene oxide with enhanced catalytic performance for hydrogen generation from formic acid","volume":"1","author":"Wang","year":"2013","journal-title":"J. Mater. Chem. A"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"28576","DOI":"10.1039\/C9RA05939C","article-title":"Microwave-assisted iodine-catalyzed oxidative coupling of dibenzyl(difurfuryl)disulfides with amines: A rapid and efficient protocol for thioamides","volume":"9","author":"Chen","year":"2019","journal-title":"RSC Adv."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"19939","DOI":"10.1016\/j.ijhydene.2018.09.036","article-title":"Magnetic graphene oxide-ionic liquid grafted chitosan composites anchored Pd(0) nanoparticles: A robust heterogeneous catalyst with enhanced activity and superior reusability for hydrogen generation from ammonia borane","volume":"43","author":"Jia","year":"2018","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"13469","DOI":"10.1039\/C3RA47974A","article-title":"Photocatalytic hydrogen generation from water using a hybrid of graphene nanoplatelets and self doped TiO2\u2013Pd","volume":"4","author":"Sayed","year":"2014","journal-title":"RSC Adv."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Li, N., Xiang, F., and Fratalocchi, A. (2021). Silicon-Based Photocatalysis for Green Chemical Fuels and Carbon Negative Technologies. Adv. Sustain. Syst., 5.","DOI":"10.1002\/adsu.202000242"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Zhang, Y., Chen, H., Wang, S., Shao, W., Qin, W., Zhao, X., and Kong, F. (2020). Facile fabrication and structure control of SiO2\/carbon via in situ doping from liquefied bio-based sawdust for supercapacitor applications. Ind. Crop. Prod., 151.","DOI":"10.1016\/j.indcrop.2020.112490"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"F148","DOI":"10.1149\/1.1375797","article-title":"Characterization of Carbon-Doped SiO2 Low k Thin Films: Preparation by Plasma-Enhanced Chemical Vapor Deposition from Tetramethylsilane","volume":"148","author":"Han","year":"2001","journal-title":"J. Electrochem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"996","DOI":"10.1557\/JMR.2004.0130","article-title":"Effects of Properties and Growth Parameters of Doped and Undoped Silicon Oxide Films on Wear Behavior During Chemical Mechanical Planarization Process","volume":"19","author":"Sikder","year":"2004","journal-title":"J. Mater. Res."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3715","DOI":"10.1063\/1.372406","article-title":"Thermal stability and breakdown strength of carbon-doped SiO2:F films prepared by plasma-enhanced chemical vapor deposition method","volume":"87","author":"Lubguban","year":"2000","journal-title":"J. Appl. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Ma, L., Wang, Y., Wang, Y., and Fu, S. (2019). Formation of C-doped SiO2 coatings on carbon fibers by the sol-dipping process. Colloids Surf. A Physicochem. Eng. Asp., 580.","DOI":"10.1016\/j.colsurfa.2019.123700"},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Zhao, L., Barbarin, Y., Croes, K., Baklanov, M.R., Verdonck, P., T\u0151kei, Z., and Claeys, C. (2015). Impact of carbon-doping on time dependent dielectric breakdown of SiO2-based films. Appl. Phys. Lett., 106.","DOI":"10.1063\/1.4913485"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2191","DOI":"10.1021\/acsami.7b16950","article-title":"Functionalization of SiO2 Surfaces for Si Monolayer Doping with Minimal Carbon Contamination","volume":"10","author":"Collins","year":"2018","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"226","DOI":"10.4028\/www.scientific.net\/MSF.734.226","article-title":"Photo-Catalytic Activity of Carbon\/Nitrogen Doped TiO2-SiO2 under UV and Visible Light Irradiation","volume":"734","author":"Mungondori","year":"2012","journal-title":"Mater. Sci. Forum"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"6167","DOI":"10.1039\/c3nr01314f","article-title":"Efficient photocatalytic activity with carbon-doped SiO2 nanoparticles","volume":"5","author":"Zhang","year":"2013","journal-title":"Nanoscale"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.diamond.2011.10.008","article-title":"Large photoconductivity of Pd doped amorphous carbon film\/SiO2\/Si","volume":"21","author":"Xue","year":"2012","journal-title":"Diam. Relat. Mater."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"4172","DOI":"10.1021\/jp312859x","article-title":"Electrocatalysis on Shape-Controlled Palladium Nanocrystals: Oxygen Reduction Reaction and Formic Acid Oxidation","volume":"117","author":"Shao","year":"2013","journal-title":"J. Phys. Chem. C"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"7","DOI":"10.1016\/j.cattod.2010.03.050","article-title":"Hydrogen from formic acid decomposition over Pd and Au catalysts","volume":"154","author":"Bulushev","year":"2010","journal-title":"Catal. Today"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"188","DOI":"10.1021\/acsenergylett.6b00574","article-title":"Formic Acid as a Hydrogen Energy Carrier","volume":"2","author":"Eppinger","year":"2017","journal-title":"ACS Energy Lett."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"819","DOI":"10.1021\/acscatal.8b04414","article-title":"Core\u2013Shell Engineering of Pd\u2013Ag Bimetallic Catalysts for Efficient Hydrogen Production from Formic Acid Decomposition","volume":"9","author":"Choi","year":"2019","journal-title":"ACS Catal."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2493","DOI":"10.1039\/C8CY02603C","article-title":"Influence of Au\/Pd alloy on an amine functionalised ZnCr LDH\u2013MCM-41 nanocomposite: A visible light sensitive photocatalyst towards one-pot imine synthesis","volume":"9","author":"Sahoo","year":"2019","journal-title":"Catal. Sci. Technol."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"13750","DOI":"10.1039\/C4CC05941G","article-title":"An ordered bcc CuPd nanoalloy synthesised via the thermal decomposition of Pd nanoparticles covered with a metal\u2013organic framework under hydrogen gas","volume":"50","author":"Li","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"4406","DOI":"10.1002\/anie.201301009","article-title":"An Efficient CoAuPd\/C Catalyst for Hydrogen Generation from Formic Acid at Room Temperature","volume":"52","author":"Wang","year":"2013","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"514","DOI":"10.1016\/j.apcatb.2014.06.004","article-title":"Carbon supported trimetallic PdNiAg nanoparticles as highly active, selective and reusable catalyst in the formic acid decomposition","volume":"160\u2013161","author":"Yurderi","year":"2014","journal-title":"Appl. Catal. B Environ."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"4242","DOI":"10.1039\/B306307K","article-title":"The electro-oxidation of formic acid on Pt\u2013Pd single crystal bimetallic surfaces","volume":"5","author":"Arenz","year":"2003","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"11417","DOI":"10.1039\/C5CC02371H","article-title":"Amine grafted silica supported CrAuPd alloy nanoparticles: Superb heterogeneous catalysts for the room temperature dehydrogenation of formic acid","volume":"51","author":"Yurderi","year":"2015","journal-title":"Chem. Commun."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"5496","DOI":"10.1016\/j.electacta.2005.03.030","article-title":"Pt\u2013Sn\/C electrocatalysts for methanol oxidation synthesized by reduction with formic acid","volume":"50","author":"Colmati","year":"2005","journal-title":"Electrochim. Acta"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"271","DOI":"10.1007\/s10562-009-9955-5","article-title":"Reaction of Formic Acid on Zn-Modified Pd(111)","volume":"130","author":"Jeroro","year":"2009","journal-title":"Catal. Lett."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"71","DOI":"10.1016\/j.jpowsour.2006.02.072","article-title":"Electro-oxidation of methanol and formic acid on PtRu and PtAu for direct liquid fuel cells","volume":"163","author":"Choi","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"16150","DOI":"10.1039\/C7TA02040F","article-title":"Formic acid dehydrogenation over Pd NPs supported on amine-functionalized SBA-15 catalysts: Structure\u2013activity relationships","volume":"5","author":"Koh","year":"2017","journal-title":"J. Mater. Chem. A"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"4737","DOI":"10.1016\/j.ijhydene.2018.12.208","article-title":"Effect of the amine group content on catalytic activity and stability of mesoporous silica supported Pd catalysts for additive-free formic acid dehydrogenation at room temperature","volume":"44","author":"Jin","year":"2019","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Farajzadeh, M., Alamgholiloo, H., Nasibipour, F., Banaei, R., and Rostamnia, S. (2020). Anchoring Pd-nanoparticles on dithiocarbamate- functionalized SBA-15 for hydrogen generation from formic acid. Sci. Rep., 10.","DOI":"10.1038\/s41598-020-75369-y"},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Jin, M.-H., Oh, D., Park, J.-H., Lee, C.-B., Lee, S.-W., Park, J.-S., Lee, K.-Y., and Lee, D.-W. (2016). Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition. Sci. Rep., 6.","DOI":"10.1038\/srep33502"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"19146","DOI":"10.1039\/c2jm32776g","article-title":"Palladium silica nanosphere-catalyzed decomposition of formic acid for chemical hydrogen storage","volume":"22","author":"Yadav","year":"2012","journal-title":"J. Mater. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"895","DOI":"10.1007\/s10570-019-02838-7","article-title":"Dimaval as an efficient ligand for binding Ru(III) on cross-linked chitosan aerogel: Synthesis, characterisation and catalytic investigation","volume":"27","author":"Keshipour","year":"2020","journal-title":"Cellulose"},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Keshipour, S., and Al-Azmi, A. (2020). Synthesis and catalytic application of Pd\/PdO\/Fe3O4@polymer-like graphene quantum dots. Appl. Organomet. Chem., 34.","DOI":"10.1002\/aoc.5311"},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Al-Azmi, A., and Keshipour, S. (2019). Cross-linked chitosan aerogel modified with Pd(II)\/phthalocyanine: Synthesis, characterization, and catalytic application. Sci. Rep., 9.","DOI":"10.1038\/s41598-019-50021-6"},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Keshipour, S., and Mohammad-Alizadeh, S. (2021). Nickel phthalocyanine@graphene oxide\/TiO2 as an efficient degradation catalyst of formic acid toward hydrogen production. Sci. Rep., 11.","DOI":"10.1038\/s41598-021-95382-z"},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Ahmadi, H., Keshipour, S., and Ahour, F. (2020). New water-soluble colorimetric pH and metal ione sensor based on graphene quantum dot modified with alizarine red S. Sci. Rep., 10.","DOI":"10.1038\/s41598-020-70821-5"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"10005","DOI":"10.1039\/C6CP00186F","article-title":"Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature","volume":"18","author":"He","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_44","first-page":"211","article-title":"An Overview of the Photocatalytic H2 Evolution by Semiconductor-Based Materials for Nonspecialists","volume":"31","author":"Teixeira","year":"2020","journal-title":"J. Braz. Chem. Soc."},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Miriam, N.G., Kohsuke, M., David, S.T., Yasutaka, K., and Hiromi, Y. (2019). New Approaches Toward the Hydrogen Production From Formic Acid Dehydrogenation Over Pd-Based Heterogeneous Catalysts. Front. Mater., 6.","DOI":"10.3389\/fmats.2019.00044"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2454","DOI":"10.1021\/jp408354r","article-title":"Influence of Silica Types on Synthesis and Performance of Amine\u2013Silica Hybrid Materials Used for CO2 Capture","volume":"118","author":"Li","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Parida, B., Choi, J., Lim, G., Kim, K., and Kim, K. (2013). Enhanced Visible Light Absorption by 3C-SiC Nanoparticles Embedded in Si Solar Cells by Plasma-Enhanced Chemical Vapor Deposition. J. Nanomater., 2013.","DOI":"10.1155\/2013\/953790"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"10379","DOI":"10.1021\/acssuschemeng.7b02388","article-title":"Mesoporous Chitosan\u2013SiO2 Nanoparticles: Synthesis, Characterization, and CO2 Adsorption Capacity","volume":"5","author":"Rafigh","year":"2017","journal-title":"ACS Sustain. Chem. Eng."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/22\/3919\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T07:29:26Z","timestamp":1760167766000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/13\/22\/3919"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,11,12]]},"references-count":48,"journal-issue":{"issue":"22","published-online":{"date-parts":[[2021,11]]}},"alternative-id":["polym13223919"],"URL":"https:\/\/doi.org\/10.3390\/polym13223919","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,11,12]]}}}