{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,23]],"date-time":"2026-06-23T19:05:09Z","timestamp":1782241509549,"version":"3.54.5"},"reference-count":55,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:00:00Z","timestamp":1760400000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100007504","name":"Istanbul Technical University","doi-asserted-by":"publisher","award":["TGA-2022-43448"],"award-info":[{"award-number":["TGA-2022-43448"]}],"id":[{"id":"10.13039\/501100007504","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>This study introduces nitrogen- and silicon-containing carbon quantum dots (N,Si-CQDs), synthesized hydrothermally from the sustainable bioresource stinging nettle (Urtica dioica L.), as chemically active supports for Pt, Pd, and Pt3Pd1 electrocatalysts. The N,Si-CQDs were characterized by a high concentration of N\/O surface functionalities and the presence of biogenic Si. A significant finding is that, with this support, biogenic Si acts as a nucleation template: Pd forms in situ as orthorhombic Pd9Si2 nanorods alongside spherical particles, whereas Pt predominantly develops as cubic\/quasi-cubic crystals. This templating process promotes faceted (cubic) Pt3Pd1 alloy nanoparticles with robust interfacial contact with the support and a log-normal size distribution (14.2 \u00b1 4.3 nm) on N,Si-CQDs (4.7 \u00b1 1.4 nm). This configuration enhanced the electrochemically active surface area to 181 m2 gPt\u22121, significantly exceeding those of commercial Pt1Pd1\/XC-72 (27.7 m2 gPt\u22121) and monometallic Pt\/N,Si-CQDs (14.3 m2 gPt\u22121). Consequently, the catalyst demonstrated superior methanol oxidation performance, evidenced by a low onset potential (0.17 V), approximately 10-fold higher mass activity compared to Pt1Pd1\/XC-72, and 53% activity retention after a 16 h accelerated durability test. The enhanced performance is attributed to the strong nanoparticle anchoring by N,Si-CQDs, the bifunctional\/ligand effects of the Pt\u2013Pd alloy that improve CO tolerance, and the templating role of biogenic Si.<\/jats:p>","DOI":"10.3390\/nano15201561","type":"journal-article","created":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T10:37:14Z","timestamp":1760438234000},"page":"1561","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Harnessing Biogenic Silica: Nanoarchitected Pt3Pd1 on Nettle-Derived N,Si-CQDs for High-Performance Methanol Electrooxidation"],"prefix":"10.3390","volume":"15","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0504-8607","authenticated-orcid":false,"given":"Seden","family":"Beyhan","sequence":"first","affiliation":[{"name":"Department of Chemistry, Faculty of Science and Letters, Istanbul Technical University, Maslak 34469, Istanbul, Turkey"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,10,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"313","DOI":"10.1016\/S0378-7753(01)01064-3","article-title":"Development of a compact 500 W class direct methanol fuel cell stack","volume":"106","author":"Dohle","year":"2002","journal-title":"J. Power Sources"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"12020","DOI":"10.1021\/j100148a030","article-title":"Methanol Electrooxidation on Well-Characterized Platinum-Ruthenium Bulk Alloys","volume":"97","author":"Gasteiger","year":"1993","journal-title":"J. Phys. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1016\/j.jpowsour.2003.09.032","article-title":"International activities in DMFC R&D: Status of technologies and potential applications","volume":"127","author":"Dillon","year":"2004","journal-title":"J. Power Sources"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"128","DOI":"10.1186\/s11671-024-04066-w","article-title":"Recent Advancements and Prospects in Noble and Non-Noble Electrocatalysts for Materials Methanol Oxidation Reactions","volume":"19","author":"Singh","year":"2024","journal-title":"Discov. Nano"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"114447","DOI":"10.1016\/j.jece.2024.114447","article-title":"Anode electrocatalysts and their supporting materials for methanol oxidation reaction based on research conducted in recent five years: Comprehensive review","volume":"12","author":"Beygisangchin","year":"2024","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2069","DOI":"10.1021\/acs.jpcc.6b11528","article-title":"Enhanced Electrocatalytic Performance of Pt3Pd1 Alloys Supported on CeO2\/C for Methanol Oxidation and Oxygen Reduction Reactions","volume":"121","author":"Yousaf","year":"2017","journal-title":"J. Phys. Chem. C"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"16522","DOI":"10.1021\/jacs.5c03118","article-title":"Tailoring Mesopores on Ultrathin Hollow Carbon Nanoarchitecture with N2O2 Coordinated Ni Single-Atom Catalysts for Hydrogen Evolution","volume":"147","author":"Kim","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"041317","DOI":"10.1063\/5.0213150","article-title":"Nanoarchitectured MOF-derived Porous Carbons: Road to Future Carbon Materials","volume":"11","author":"Kim","year":"2024","journal-title":"Appl. Phys. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2990","DOI":"10.1038\/s41596-022-00718-2","article-title":"MOF-derived nanoporous carbons with diverse tunable nanoarchitectures","volume":"17","author":"Kim","year":"2022","journal-title":"Nat. Protoc."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"332","DOI":"10.1016\/j.electacta.2016.07.119","article-title":"Platinum\/nitrogen-doped carbon nanoparticles synthesized in nitrogen-doped carbon quantum dots aqueous solution for methanol electro-oxidation","volume":"213","author":"Zhang","year":"2016","journal-title":"Electrochim. Acta"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"100276","DOI":"10.1016\/j.cartre.2023.100276","article-title":"Properties, synthesis, and applications of carbon dots: A review","volume":"12","author":"Ozyurt","year":"2023","journal-title":"Carbon Trends"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"279","DOI":"10.1016\/j.jechem.2020.06.057","article-title":"Carbon quantum dots for advanced electrocatalysis","volume":"55","author":"Tian","year":"2021","journal-title":"J. Energy Chem."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Wang, X., Feng, Y., Dong, P., and Huang, J. (2019). A Mini Review on Carbon Quantum Dots: Preparation, Properties, and Electrocatalytic Application. Front. Chem., 7.","DOI":"10.3389\/fchem.2019.00671"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/j.jpowsour.2015.04.150","article-title":"Multiwall-carbon nanotube modified by N-doped carbon quantum dots as Pt catalyst support for methanol electrooxidation","volume":"289","author":"Zhang","year":"2015","journal-title":"J. Power Sources"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"6797","DOI":"10.1021\/am500403n","article-title":"Si-Doped Carbon Quantum Dots: A Facile and General Preparation Strategy, Bioimaging Application, and Multifunctional Sensor","volume":"6","author":"Qian","year":"2014","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"6830","DOI":"10.1016\/j.ijhydene.2013.03.058","article-title":"Promising Anode Candidates for Direct Ethanol Fuel Cell: Carbon Supported PtSn-Based Trimetallic Catalysts Prepared by B\u00f6nnemann Method","volume":"38","author":"Beyhan","year":"2013","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"305","DOI":"10.1016\/j.apcatb.2012.11.007","article-title":"Pronounced synergetic effect of the nano-sized PtSnNi\/C catalyst for ethanol oxidation in direct ethanol fuel cell","volume":"130\u2013131","author":"Beyhan","year":"2013","journal-title":"Appl. Catal. B Environ."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1045","DOI":"10.1016\/j.electacta.2003.10.015","article-title":"Nano-stuctured Pt\u2013Fe\/C as cathode catalyst in direct methanol fuel cell","volume":"49","author":"Li","year":"2004","journal-title":"Electrochim. Acta"},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Nguyen, K.G., Baragau, I.-A., Gromicova, R., Nicolaev, A., Thomson, S.A.J., Rennie, A., Power, N.P., Sajjad, M.T., and Kellici, S. (2022). Investigating the effect of N-doping on carbon quantum dots structure, optical properties and metal ion screening. Sci. Rep., 12.","DOI":"10.1038\/s41598-022-16893-x"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"165","DOI":"10.3762\/bjnano.14.17","article-title":"Structural, optical, and bioimaging characterization of carbon quantum dots solvothermally synthesized from o-phenylenediamine","volume":"14","author":"Budimir","year":"2023","journal-title":"Beilstein J. Nanotechnol."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"28","DOI":"10.1016\/j.jcis.2014.09.013","article-title":"Carbon Dots Functionalized by Organosilane with Double-Sided Anchoring for Nanomolar Hg2+ Detection","volume":"437","author":"Wang","year":"2015","journal-title":"J. Colloid Interface Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"805","DOI":"10.1007\/s00604-013-1153-x","article-title":"Silicon-hybrid carbon dots strongly enhance the chemiluminescence of luminol","volume":"181","author":"Lin","year":"2014","journal-title":"Microchim. Acta"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1639","DOI":"10.1039\/c3cc38486a","article-title":"Photoluminescent organosilane-functionalized carbon dots as temperature probes","volume":"49","author":"Chen","year":"2013","journal-title":"Chem. Commun."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"109487","DOI":"10.1016\/j.jece.2023.109487","article-title":"Preparation of photocatalysts decorated by carbon quantum dots (CQDs) and their applications: A review","volume":"11","author":"Zhao","year":"2023","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4196","DOI":"10.1166\/jnn.2018.15206","article-title":"High Quality Nitrogen and Silicon Co-Doped Carbon Dots (N\/Si\u2013CDs) for Fe3+ Sensing","volume":"18","author":"Wu","year":"2018","journal-title":"J. Nanosci. Nanotechnol."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Shen, F., Lu, Z., Yan, K., Luo, K., Pei, S., and Xiang, P. (2025). Synthesis and properties of carbon quantum dots as an antimicrobial agent and detection of ciprofloxacin. Sci. Rep., 15.","DOI":"10.1038\/s41598-025-14383-4"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"110730","DOI":"10.1016\/j.materresbull.2019.110730","article-title":"Facile synthesis of novel carbon quantum dots from biomass waste for highly sensitive detection of iron ions","volume":"124","author":"Wang","year":"2020","journal-title":"Mater. Res. Bull."},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Liu, P., Ga, L., Wang, Y., and Ai, J. (2023). Synthesis of temperature sensing nitrogen-doped carbon dots and their application in fluorescent ink. Molecules, 28.","DOI":"10.3390\/molecules28186607"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"31098","DOI":"10.1021\/acsnano.4c08291","article-title":"Probing Active Sites on Pd\/Pt Alloy Nanoparticles by CO Adsorption","volume":"18","author":"Dolling","year":"2024","journal-title":"ACS Nano"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"707","DOI":"10.1021\/ic502394u","article-title":"Solution Synthesis of Metal Silicide Nanoparticles","volume":"54","author":"McEnaney","year":"2015","journal-title":"Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"8195","DOI":"10.1039\/c2jm30411b","article-title":"Anisotropic Growth of Palladium Twinned Nanostructures Controlled by Kinetics and Their Unusual Activities in Galvanic Replacement","volume":"22","author":"Wang","year":"2012","journal-title":"J. Mater. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1007\/BF03036932","article-title":"DFT Studies of the Characteristics of Pd\u2013Pt Core\u2013Shell Clusters","volume":"34","author":"Okumura","year":"2008","journal-title":"Res. Chem. Intermed."},{"key":"ref_33","first-page":"907","article-title":"Construction of dendritic Pt\u2013Pd bimetallic nanotubular heterostructure for advanced oxygen reduction","volume":"3","author":"Wang","year":"2024","journal-title":"Interdiscip. Mater."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"154702","DOI":"10.1063\/1.4898086","article-title":"Oxidation of palladium on Au(111) and ZnO(0001) supports","volume":"141","author":"Lallo","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Wang, R., Lou, M., Zhang, J., Sun, Z., Li, Z., and Wen, P. (2021). ZIF-8@ZIF-67-Derived Co Embedded into Nitrogen-Doped Carbon Nanotube Hollow Porous Carbon Supported Pt as an Efficient Electrocatalyst for Methanol Oxidation. Nanomaterials, 11.","DOI":"10.3390\/nano11102491"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"23582","DOI":"10.1021\/acs.langmuir.5c02700","article-title":"Precisely Engineered Nitrogen Dopants in Pd\/NC Catalysts: Synergistic Pyridinic\u2013Pyrrolic\u2013Graphitic Triad for Alkaline Methanol Electrooxidation","volume":"41","author":"Guo","year":"2025","journal-title":"Langmuir"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1170","DOI":"10.1021\/am506916y","article-title":"Metal\u2013Support Interaction in Platinum and Palladium Nanoparticles Loaded on Nitrogen-Doped Mesoporous Carbon for Oxygen Reduction Reaction","volume":"7","author":"Perini","year":"2015","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"F252","DOI":"10.1149\/2.045403jes","article-title":"Kinetic and Mechanistic Investigation of Methanol Oxidation on a Smooth Polycrystalline Pt Surface","volume":"161","author":"Hou","year":"2014","journal-title":"J. Electrochem. Soc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"100522","DOI":"10.1039\/C5RA14682H","article-title":"Halide-Aided Controlled Fabrication of Pt\u2013Pd\/Graphene Bimetallic Nanocomposites for Methanol Electrooxidation","volume":"5","author":"Reddy","year":"2015","journal-title":"RSC Adv."},{"key":"ref_40","doi-asserted-by":"crossref","unstructured":"Xiang, L., Hu, Y., Zhao, Y., Cao, S., and Kuai, L. (2023). Carbon-Supported High-Loading Sub-4 nm PtCo Alloy Electrocatalysts for Superior Oxygen Reduction Reaction. Nanomaterials, 13.","DOI":"10.20944\/preprints202305.2253.v1"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"100","DOI":"10.1016\/j.jcat.2017.02.011","article-title":"Electron Transfer Dependent Catalysis of Pt on N-Doped Carbon Nanotubes: Effects of Synthesis Method on Metal\u2013Support Interaction","volume":"348","author":"Ning","year":"2017","journal-title":"J. Catal."},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Osman, S.H., Kamarudin, S.K., Basri, S., and Karim, N.A. (2023). Potential of 3D Hierarchical Porous TiO2-Graphene Aerogel (TiO2-GA) as Electrocatalyst Support for Direct Methanol Fuel Cells. Nanomaterials, 13.","DOI":"10.3390\/nano13121819"},{"key":"ref_43","doi-asserted-by":"crossref","unstructured":"Wang, S., Ma, L., Song, D., and Yang, S. (2023). Au Doping PtNi Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation Reaction. Nanomaterials, 13.","DOI":"10.3390\/nano13212855"},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Tate, G.L., Mehrabadi, B.A.T., Xiong, W., Kenvin, A., and Monnier, J.R. (2021). Synthesis of Highly Active Pd@Cu\u2013Pt\/C Methanol Oxidation Electrocatalysts via Continuous, Co-Electroless Deposition. Nanomaterials, 11.","DOI":"10.3390\/nano11030793"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"2203","DOI":"10.3390\/nano5042203","article-title":"Hydrothermal Synthesis of Ultrasmall Pt Nanoparticles as Highly Active Electrocatalysts for Methanol Oxidation","volume":"5","author":"Ji","year":"2015","journal-title":"Nanomaterials"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"120","DOI":"10.1016\/j.apcatb.2019.04.023","article-title":"Surface Ru enriched structurally ordered intermetallic PtFe@PtRuFe core\u2013shell nanostructure boosts methanol oxidation reaction catalysis","volume":"252","author":"Wang","year":"2019","journal-title":"Appl. Catal. B Environ."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"23046","DOI":"10.1021\/acsami.0c06460","article-title":"Tunable hollow Pt@Ru dodecahedra via galvanic replacement for efficient methanol oxidation","volume":"12","author":"Bai","year":"2020","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"119135","DOI":"10.1016\/j.apcatb.2020.119135","article-title":"Concave PtCo nanocrosses for methanol oxidation reaction","volume":"277","author":"Li","year":"2020","journal-title":"Appl. Catal. B Environ."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"282","DOI":"10.1016\/j.jcat.2020.12.034","article-title":"Pt3Mn alloy nanostructure with high-index facets by Sn doping modified for highly catalytic active electro-oxidation reactions","volume":"395","author":"Li","year":"2021","journal-title":"J. Catal."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"35240","DOI":"10.1016\/j.ijhydene.2023.05.283","article-title":"Synthesis of alloyed PtPd nanowires and study on their electro-catalytic performance to methanol oxidation reaction","volume":"48","author":"Dong","year":"2023","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"2400981","DOI":"10.1002\/admi.202400981","article-title":"Nano-Octahedron Cobalt Oxide Decorated Graphene Nanocomposites for the Selective\/Simultaneous Detection of Dopamine","volume":"12","author":"Dharmalingam","year":"2025","journal-title":"Adv. Mater. Interfaces"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2780","DOI":"10.1021\/jacsau.3c00343","article-title":"Subsurface Hydride Formation Leads to Slow Surface Adsorption Processes on a Pd(111) Single-Crystal Electrode in Acidic Electrolytes","volume":"3","author":"Chen","year":"2023","journal-title":"JACS Au"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"832","DOI":"10.1021\/cs300024h","article-title":"Degradation mechanisms of platinum electrocatalysts under realistic fuel cell conditions","volume":"2","author":"Meier","year":"2012","journal-title":"ACS Catal."},{"key":"ref_54","doi-asserted-by":"crossref","unstructured":"Yu, R., Zhang, Y., Deng, S., Zhu, R., Zhang, S., Zhang, J., Zhao, Y., and Xia, Z. (2024). Platinum Alloys for Methanol Oxidation Electrocatalysis: Reaction Mechanism and Rational Design of Catalysts with Exceptional Activity and Stability. Catalysts, 14.","DOI":"10.3390\/catal14010060"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"588","DOI":"10.1016\/j.jpowsour.2009.06.073","article-title":"A Review of Platinum-Based Catalyst Layer Degradation in Proton Exchange Membrane Fuel Cells","volume":"194","author":"Zhang","year":"2009","journal-title":"J. Power Sources"}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/20\/1561\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T11:40:21Z","timestamp":1760442021000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/20\/1561"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,14]]},"references-count":55,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2025,10]]}},"alternative-id":["nano15201561"],"URL":"https:\/\/doi.org\/10.3390\/nano15201561","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,10,14]]}}}