{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,11]],"date-time":"2025-11-11T13:42:34Z","timestamp":1762868554534,"version":"build-2065373602"},"reference-count":64,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2021,7,9]],"date-time":"2021-07-09T00:00:00Z","timestamp":1625788800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Fund of Scientific Research Flanders (FWO)","award":["1261721N"],"award-info":[{"award-number":["1261721N"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>Immobilization of two single transition metal (TM) atoms on a substrate host opens numerous possibilities for catalyst design. If the substrate contains more than one vacancy site, the combination of TMs along with their distribution patterns becomes a design parameter potentially complementary to the substrate itself and the bi-metal composition. By means of DFT calculations, we modeled three dissimilar bi-metal atoms (Ti, Mn, and Cu) doped into the six porphyrin-like cavities of porous C24N24 fullerene, considering different bi-metal distribution patterns for each binary complex, viz. TixCuz@C24N24, TixMny@C24N24, and MnyCuz@C24N24 (with x, y, z = 0\u20136). We elucidate whether controlling the distribution of bi-metal atoms into the C24N24 cavities can alter their catalytic activity toward CO2, NO2, H2, and N2 gas capture. Interestingly, Ti2Mn4@C24N24 and Ti2Cu4@C24N24 complexes showed the highest activity and selectively toward gas capture. Our findings provide useful information for further design of novel few-atom carbon-nitride-based catalysts.<\/jats:p>","DOI":"10.3390\/nano11071794","type":"journal-article","created":{"date-parts":[[2021,7,9]],"date-time":"2021-07-09T10:50:38Z","timestamp":1625827838000},"page":"1794","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Linking Bi-Metal Distribution Patterns in Porous Carbon Nitride Fullerene to Its Catalytic Activity toward Gas Adsorption"],"prefix":"10.3390","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3083-6816","authenticated-orcid":false,"given":"Parisa","family":"Nematollahi","sequence":"first","affiliation":[{"name":"Research Group Plasmant, NANO Lab Center of Excellence, Department of Chemistry, University of Antwerp, 2610 Antwerp, Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Erik C.","family":"Neyts","sequence":"additional","affiliation":[{"name":"Research Group Plasmant, NANO Lab Center of Excellence, Department of Chemistry, University of Antwerp, 2610 Antwerp, Belgium"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1016\/j.carbon.2014.04.005","article-title":"Carbon as catalyst and support for electrochemical energy conversion","volume":"75","author":"Trogadas","year":"2014","journal-title":"Carbon"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"26479","DOI":"10.1021\/jp506538d","article-title":"Porous graphitic carbon nitride: A possible metal-free photocatalyst for water splitting","volume":"118","author":"Srinivasu","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"838","DOI":"10.1021\/acssuschemeng.8b04462","article-title":"Phosphorus-doped graphene as a metal-free material for thermochemical water reforming at unusually mild conditions","volume":"7","author":"Albero","year":"2018","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"118579","DOI":"10.1016\/j.apcatb.2019.118579","article-title":"Advances in photocatalysis based on fullerene C60 and its derivatives: Properties, mechanism, synthesis, and applications","volume":"265","author":"Pan","year":"2020","journal-title":"Appl. Catal. B Environ."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/s41467-019-09545-8","article-title":"On demand synthesis of hollow fullerene nanostructures","volume":"10","author":"Han","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"043205","DOI":"10.1103\/PhysRevA.76.043205","article-title":"First- and second-electron affinities ofC60andC70isomers","volume":"76","author":"Zettergren","year":"2007","journal-title":"Phys. Rev. A"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"e1904177","DOI":"10.1002\/adma.201904177","article-title":"Carbon-based nanocages: A new platform for advanced energy storage and conversion","volume":"32","author":"Wu","year":"2020","journal-title":"Adv. Mater."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"353","DOI":"10.1016\/j.apsusc.2016.04.037","article-title":"Density functional investigation of CO and NO adsorption on TM-decorated C60 fullerene","volume":"383","year":"2016","journal-title":"Appl. Surf. Sci."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"17944","DOI":"10.1016\/j.ijhydene.2016.08.043","article-title":"Fullerene applications in fuel cells: A review","volume":"41","author":"Coro","year":"2016","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"393","DOI":"10.1016\/j.carbon.2016.12.028","article-title":"Doped fullerene as a metal-free electrocatalyst for oxygen reduction reaction: A first-principles study","volume":"114","author":"Wang","year":"2017","journal-title":"Carbon"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"151","DOI":"10.1016\/j.apsusc.2017.01.135","article-title":"Fullerene (C60)\/CdS nanocomposite with enhanced photocatalytic activity and stability","volume":"403","author":"Cai","year":"2017","journal-title":"Appl. Surf. Sci."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"753","DOI":"10.1002\/cphc.201701171","article-title":"Electrochemical properties of boron-doped fullerene derivatives for lithium-ion battery ap-plications","volume":"19","author":"Sood","year":"2018","journal-title":"ChemPhysChem"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"2839","DOI":"10.1039\/c3ee41444b","article-title":"Doping carbons beyond nitrogen: An overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications","volume":"6","author":"Paraknowitsch","year":"2013","journal-title":"Energy Environ. Sci."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"53","DOI":"10.1016\/j.carbon.2017.10.007","article-title":"Probing the activity of pure and N-doped fullerenes towards oxygen reduction reaction by density functional theory","volume":"126","author":"Chen","year":"2018","journal-title":"Carbon"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"225503","DOI":"10.1103\/PhysRevLett.87.225503","article-title":"Cross-linked nano-onions of carbon nitride in the solid phase: Existence of a novel C 48 N 12 Aza-fullerene","volume":"87","author":"Hultman","year":"2001","journal-title":"Phys. Rev. Lett."},{"key":"ref_16","first-page":"865","article-title":"Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation","volume":"454","author":"Otero","year":"2008","journal-title":"Nat. Cell Biol."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"5401","DOI":"10.1021\/nl2031037","article-title":"Nitrogen-doped graphene: Efficient growth, structure, and electronic properties","volume":"11","author":"Usachov","year":"2011","journal-title":"Nano Lett."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"12038","DOI":"10.1039\/C9TA01768B","article-title":"Direct growth of nitrogen-doped graphene films on glass by plasma-assisted hot filament CVD for enhanced electricity generation","volume":"7","author":"Zhai","year":"2019","journal-title":"J. Mater. Chem. A"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2192","DOI":"10.1021\/jp035876h","article-title":"Mass spectrometric and computational studies of heterofullerenes ([C58Pt]-, [C59Pt]+) Obtained by laser ablation of electrochemically deposited films","volume":"108","author":"Hayashi","year":"2004","journal-title":"J. Phys. Chem. A"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"9969","DOI":"10.1021\/jp2016853","article-title":"Doping of calcium in C60Fullerene for enhancing CO2Capture and N2O transformation: A theoretical study","volume":"115","author":"Gao","year":"2011","journal-title":"J. Phys. Chem. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"77","DOI":"10.1016\/j.jcat.2020.05.009","article-title":"Atomically embedded asymmetrical dual-metal dimers on N-doped graphene for ultra-efficient nitrogen reduction reaction","volume":"388","author":"He","year":"2020","journal-title":"J. Catal."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"147466","DOI":"10.1016\/j.apsusc.2020.147466","article-title":"Single transition metal atoms on nitrogen-doped carbon for CO2 electrocatalytic reduction: CO production or further CO reduction?","volume":"533","author":"Guo","year":"2020","journal-title":"Appl. Surf. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"144155","DOI":"10.1016\/j.apsusc.2019.144155","article-title":"Single cobalt atom anchored on N-doped graphyne for boosting the overall water splitting","volume":"502","author":"Gao","year":"2020","journal-title":"Appl. Surf. Sci."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/j.joule.2019.12.002","article-title":"Iron-nitrogen-carbon catalysts for proton exchange membrane fuel cells","volume":"4","author":"Asset","year":"2020","journal-title":"Joule"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"143618","DOI":"10.1016\/j.apsusc.2019.143618","article-title":"Direct methane conversion to methanol on M and MN4 embedded graphene (M=Ni and Si): A comparative DFT study","volume":"496","author":"Nematollahi","year":"2019","journal-title":"Appl. Surf. Sci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"8136","DOI":"10.1021\/acssuschemeng.8b05729","article-title":"RuN4 doped graphene oxide, a highly efficient bifunctional catalyst for oxygen reduction and CO2 reduction from computational study","volume":"7","author":"Liu","year":"2019","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3082","DOI":"10.1021\/acscatal.8b04609","article-title":"Enhanced oxygen reduction reaction on Fe\/N\/C catalyst in acetate buffer electrolyte","volume":"9","author":"Silvioli","year":"2019","journal-title":"ACS Catal."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1007\/s40820-020-00456-8","article-title":"Atomically dispersed Fe-N4 modified with precisely located S for highly efficient oxygen reduction","volume":"12","author":"Jia","year":"2020","journal-title":"Nano-Micro Lett."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"479","DOI":"10.1126\/science.aan2255","article-title":"Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst","volume":"357","author":"Chung","year":"2017","journal-title":"Science"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"259","DOI":"10.1038\/s41929-019-0237-3","article-title":"Fe\u2013N\u2013C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells","volume":"2","author":"Wan","year":"2019","journal-title":"Nat. Catal."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1038\/s41467-017-01100-7","article-title":"Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction","volume":"8","author":"Zitolo","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Kattel, S., and Wang, G. (2013). A density functional theory study of oxygen reduction reaction on Me\u2013N4 (Me = Fe, Co, or Ni) clusters between graphitic pores. J. Mater. Chem. A, 1.","DOI":"10.1039\/c3ta12142a"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"17378","DOI":"10.1021\/jp3044708","article-title":"Density functional theory study of Ni\u2013Nx\/C electrocatalyst for oxygen reduction in al-kaline and acidic media","volume":"116","author":"Kattel","year":"2012","journal-title":"J. Phys. Chem. C."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3977","DOI":"10.1021\/jacs.8b12973","article-title":"Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries","volume":"141","author":"Du","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"e1706617","DOI":"10.1002\/adma.201706617","article-title":"Surface immobilization of transition metal ions on nitrogen-doped graphene realizing high-efficient and selective CO2 reduction","volume":"30","author":"Bi","year":"2018","journal-title":"Adv. Mater."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"6930","DOI":"10.1021\/acsnano.7b02148","article-title":"Single-atomic ruthenium catalytic sites on nitrogen-doped graphene for oxygen reduction reaction in acidic medium","volume":"11","author":"Zhang","year":"2017","journal-title":"ACS Nano"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"023107","DOI":"10.1063\/1.3533909","article-title":"High-capacity hydrogen storage medium: Ti doped fullerene","volume":"98","author":"Guo","year":"2011","journal-title":"Appl. Phys. Lett."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"16271","DOI":"10.1016\/j.ijhydene.2015.05.159","article-title":"Transition metal Ti coated porous fullerene C24B24: Potential material for hydrogen storage","volume":"40","author":"Tang","year":"2015","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"7390","DOI":"10.1016\/j.ijhydene.2020.11.254","article-title":"Sc\/Ti decorated novel C24N24 cage: Promising hydrogen storage materials","volume":"46","author":"Ma","year":"2021","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2278","DOI":"10.1016\/j.ijhydene.2016.12.017","article-title":"Exploring metal decorated porphyrin-like porous fullerene as catalyst for oxygen re-duction reaction: A DFT study","volume":"42","author":"Modak","year":"2017","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"190","DOI":"10.1016\/j.inoche.2019.06.014","article-title":"Computational mechanistic insights into CO oxidation reaction over Fe decorated C24N24 fullerene","volume":"106","author":"Shakerzadeh","year":"2019","journal-title":"Inorg. Chem. Commun."},{"key":"ref_42","unstructured":"Ogliaro, F., Bearpark, M., Heyd, J., Brothers, E., Kudin, K., Staroverov, V., Keith, T., Kobayashi, R., Normand, J., and Raghavachari, K. (2016). Gaussian 16, Gaussian, Inc.. Revision A. 03."},{"key":"ref_43","unstructured":"Lide, D.R. (2004). CRC Handbook of Chemistry and Physics, CRC Press."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"151102","DOI":"10.1063\/1.4898430","article-title":"Communication: A combined periodic density functional and incremental wave-function-based approach for the dispersion-accounting time-resolved dynamics of 4He nanodroplets on surfaces: 4He\/graphene","volume":"141","author":"Stoll","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"25184","DOI":"10.1021\/jp3047517","article-title":"Transition metal decorated porphyrin-like porous fullerene: Promising materials for molecular hydrogen adsorption","volume":"116","author":"Srinivasu","year":"2012","journal-title":"J. Phys. Chem. C"},{"key":"ref_46","unstructured":"Ochterski, J.W. (2000). Thermochemistry in Gaussian, Gaussian Inc."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"1083","DOI":"10.1016\/0040-4020(68)88057-3","article-title":"Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane","volume":"24","author":"Wiberg","year":"1968","journal-title":"Tetrahedron"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1016\/j.ijleo.2017.01.096","article-title":"How the alkali metal atoms affect electronic structure and the nonlinear optical properties of C24N24 nanocage","volume":"135","author":"Song","year":"2017","journal-title":"Optik"},{"key":"ref_49","doi-asserted-by":"crossref","unstructured":"Holcomb, D., and Kittel, C. (1967). Introduction to solid state physics. Am. J. Phys., 35.","DOI":"10.1119\/1.1974177"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"5326","DOI":"10.1103\/PhysRevB.54.5326","article-title":"Cohesive energy of 3D transition metals: Density functional theory atomic and bulk calculations","volume":"54","author":"Philipsen","year":"1996","journal-title":"Phys. Rev. B"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"303","DOI":"10.1016\/j.jechem.2020.04.014","article-title":"Fe, V-co-doped C2N for electrocatalytic N2-to-NH3 conversion","volume":"53","author":"Wei","year":"2021","journal-title":"J. Energy Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"228306","DOI":"10.1016\/j.jpowsour.2020.228306","article-title":"Synergistic effects of Pd\u2013Ag bimetals and g-C3N4 photocatalysts for selective and efficient conversion of gaseous CO2","volume":"466","author":"Wang","year":"2020","journal-title":"J. Power Sources"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"3117","DOI":"10.1002\/cphc.201700529","article-title":"A review on bimetallic nickel-based catalysts for CO2 reforming of methane","volume":"18","author":"Bian","year":"2017","journal-title":"ChemPhysChem"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"6222","DOI":"10.1021\/jp210555s","article-title":"Bimetallic Au\u2013Pd alloy catalysts for N2O decomposition: Effects of surface structures on catalytic activity","volume":"116","author":"Wei","year":"2012","journal-title":"J. Phys. Chem. C."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"2170","DOI":"10.1021\/jp407940z","article-title":"Carbon dioxide capture and gas separation on B80Fullerene","volume":"118","author":"Sun","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"420","DOI":"10.1016\/j.apsusc.2016.11.157","article-title":"Enhanced CO2 capture on graphene via N, S dual-doping","volume":"399","author":"Li","year":"2017","journal-title":"Appl. Surf. Sci."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.jcou.2019.08.014","article-title":"Investigating CO2 storage properties of C2N monolayer functionalized with small metal clusters","volume":"35","author":"Deshpande","year":"2020","journal-title":"J. CO2 Util."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"15256","DOI":"10.1016\/j.ijhydene.2017.04.256","article-title":"Transition metal atom Fe, Co, Ni decorated B38 fullerene: Potential material for hydrogen storage","volume":"42","author":"Liu","year":"2017","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"4154","DOI":"10.1016\/j.ijhydene.2020.10.161","article-title":"High capacity reversible hydrogen storage in titanium doped 2D carbon allotrope \u03a8-graphene: Density Functional Theory investigations","volume":"46","author":"Chakraborty","year":"2021","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"143987","DOI":"10.1016\/j.apsusc.2019.143987","article-title":"Uncovering the electrochemical mechanisms for hydrogen evolution reaction of heteroatom doped M2C MXene (M = Ti, Mo)","volume":"500","author":"Ding","year":"2020","journal-title":"Appl. Surf. Sci."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"896","DOI":"10.1016\/j.cej.2019.03.037","article-title":"Molten salt assistant synthesis of three-dimensional cobalt doped graphitic carbon nitride for photocatalytic N2 fixation: Experiment and DFT simulation analysis","volume":"368","author":"Wang","year":"2019","journal-title":"Chem. Eng. J."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"13790","DOI":"10.1039\/C8TA03989E","article-title":"Fe-doped phosphorene for the nitrogen reduction reaction","volume":"6","author":"Wei","year":"2018","journal-title":"J. Mater. Chem. A"},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"148012","DOI":"10.1016\/j.apsusc.2020.148012","article-title":"Theoretical insights into the performance of single and double transition metal atoms doped on N-graphenes for N2 electroreduction","volume":"537","author":"Qu","year":"2021","journal-title":"Appl. Surf. Sci."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"166","DOI":"10.1097\/00010694-195308000-00014","article-title":"The Dynamical Character of Adsorption","volume":"76","author":"DeBoer","year":"1953","journal-title":"Soil Sci."}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/11\/7\/1794\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:28:30Z","timestamp":1760164110000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/11\/7\/1794"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,9]]},"references-count":64,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2021,7]]}},"alternative-id":["nano11071794"],"URL":"https:\/\/doi.org\/10.3390\/nano11071794","relation":{},"ISSN":["2079-4991"],"issn-type":[{"type":"electronic","value":"2079-4991"}],"subject":[],"published":{"date-parts":[[2021,7,9]]}}}