Graphitic carbon nitrides as platforms for single-atom photocatalysis: moving towards design principles for improved performance

• Grant number: 20/14741-6
• Support Opportunities: Research Grants - Young Investigators Grants
• Start date: December 01, 2021
• End date: November 30, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Ivo Freitas Teixeira
• Grantee: Ivo Freitas Teixeira
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• Associated researchers: José Maria Correa Bueno ; Lucia Helena Mascaro Sales ; Markus Antonietti
• Associated research grant(s): 24/07802-0 - Phenol-Formaldehyde Microballoons as Heterogeneous Photocatalyst for Chemical Production, AP.R SPRINT; 24/00839-5 - Single Atoms supported on N-doped carbon: A Novel Platform for Single Atom Catalysis, AP.R; 22/14209-8 - Heterogeneous single-atom based catalysts to chemo/photo-catalytic depolymerization: a route to circular polymer economy, AP.R SPRINT; 21/14792-2 - Epoxidation of vegetable oil's double bonds by nickel single-atoms stabilized in graphitic carbon nitrides: sustainable monomers for epoxy thermoset polymer composites, AP.R SPRINT; 21/11162-8 - Multi-user equipment approved in grant 2020/14741-6: GC-MS/FID/TCD (2 injetores+Loop+Sistema valvulado), AP.EMU
• Associated scholarship(s): 24/15274-3 - Selective photo-oxidation of methane to formic acid guided by visible light and FeCl3, BP.IC; 24/12042-4 - Chiral Carbon Nitride as (Photo)Catalyst Towards Fine Chemical Synthesis, BP.DR; 24/02739-8 - Single Atoms Supported on N-doped Carbon and Carbon Nitrides: Strategic Materials for Application in Energy Storage Systems, BP.DR; + associated scholarships 24/15825-0 - Photocatalytic Chlorination of C-H Bonds Using Crystalline Carbon Nitrides, BP.IC; 24/06583-2 - Development of Carbon Nitride Membranes for Sustainable Water Desalination, BP.IC; 23/06070-2 - Toluene Selective Photo-Oxidation Using Graphitic Carbon Nitride as a Catalyst, BP.MS; 23/13283-2 - Photocatalysts with Single-Atoms Supported on Carbon Nitride for Hydrogen Transfer Reactions, BP.IC; 23/13463-0 - Green Hydrogen Production Employing Nickel Poly (Heptazine Imide) Photocatalysts: A Low-Cost Catalyst for H2 Evolution, BP.IC; 23/06210-9 - PHI single-atoms photocatalysts applied to oxidation and reduction reactions, BP.DR; 23/10973-8 - Single-Atoms Stabilized in Poly(Heptazine Imides): Photocatalytic Production and Detection of Ammonia, BP.IC; 22/14652-9 - Photoreduction reactions to sustainable production of chemical commodities: a solar to chemical strategy, BP.DR; 23/03714-6 - Single Atoms Supported on Crystalline Carbon Nitrides Catalysts for Selective Benzene Oxidation to Phenol, BP.IC; 22/12084-3 - PHI/PTI-Single-Atoms Photocatalysts Applied to Biomass Conversion, BP.MS; 22/14335-3 - Graphitic Carbon Nitrides as Platforms for Single-Atom Photocatalysis: Moving Towards Design Principles for Improved Performance, BP.IC; 22/13249-6 - Graphitic carbon nitrides as platforms for single-atom photocatalysis: moving towards design principles for improved performance, BP.DD; 22/04748-9 - Graphitic carbon nitrides as acid solid catalysts applied to biomass conversion, BP.MS; 22/06136-0 - Graphitic Carbon Nitrides as Platforms for Single-Atom Photocatalysis: Moving Towards Design Principles for Improved Performance, BP.TT; 21/13271-9 - Single atoms coordinated on graphitic carbon nitrides to photocatalytic conversion of methane, BP.DR; 21/13432-2 - Photooxidation of fluoride for C-F and S-F bond formation, BP.IC; 21/14006-7 - PHI/PTI-single-atoms controlled synthesis and energy applications, BP.DD - associated scholarships

Abstract

This young investigator proposal aims to create a research group of excellence focused on the field of Single-Atom Catalysis (SAC) in Brazil, based on the Department of Chemistry at the Federal University of São Carlos (DQ-UFSCar). Although the DQ-UFSCar presents research groups established in several areas, including nanomaterials and catalysis, the department does not have groups focused on the growing area of heterogeneous catalysis/photocatalysis, based on Single-Atoms catalysts (SAC). As far as we know, there is no research group focused on Single-Atom Catalysis in Brazil and according to the FAPESP library, there is no research project being funded on this topic. The candidate intends to fill this gap and, at the same time, work closely with established research groups, with complementary infrastructure and expertise in DQ-UFSCar and DEQ-UFSCar. The activities of the research group proposed here will cover the design and controlled synthesis of heterogeneous photocatalysts with Single-Atoms, their photocatalytic applications, development of new characterization techniques for SACs and the investigation of their mechanisms of activity. Specifically, our proposal is focused on the controlled synthesis and use of graphite carbon nitrides (PHI and PTI) as hosts for Single-Atoms of different metals, once the Single-Atoms are stabilized, they will be applied in photocatalytic reactions. The research project is divided into 4 parts: (I) design and controlled synthesis of Single-Atoms catalysts; (II) photocatalytic applications for energy conversion (especially, water photolysis, CO2 reduction, CH4 oxidation), organic synthesis (for example, photoredox reactions, Susuki coupling, and C-H activation) and biomass conversion; (III) investigation of the photocatalytic mechanisms behind the activity of the systems; (IV) combine this knowledge to retro-design the synthesis of photocatalytic systems based on "Single-Atoms" in order to improve their properties and efficiencies. The proposed project is very interdisciplinary and will be performed in close collaboration with a range of research groups in Brazil and abroad. (AU)

Scientific publications

(18)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

ROGOLINO, ANDREA; FILHO, JOSE B. G.; FRITSCH, LORENA; ARDISSON, JOSE D.; DA SILVA, MARCOS A. R.; ATTA DIAB, GABRIEL ALI; SILVA, INGRID FERNANDES; FERREIRA MORAES, CARLOS ANDREE; FORIM, MOACIR ROSSI; BAUER, MATTHIAS; et al. Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions. ACS CATALYSIS, v. 13, n. 13, p. 8-pg., 2023-06-15. (21/14006-7, 21/13271-9, 20/14741-6, 21/11162-8)

OLIVEIRA, WANESSA L.; OLIVEIRA, EDUARDA FERREIRA DE; BATISTA, WALKER VINICIUS FERREIRA DO CARMO; MOURA, HENRIQUE A. J. L.; PIRES, MANOEL JOSE MENDES; COELHO, RAFAEL MENDES; DIAB, GABRIEL ALI ATTA; TEIXEIRA, IVO FREITAS; MARQUES, GLEISON; MASTELARO, VALMOR ROBERTO; et al. A metal-free catalyst based on g-C3N4 functionalized with cyamelurate-like groups: Catalytic properties and mechanism of a new heterogeneous Fenton-like catalyst. Carbon, v. 214, p. 12-pg., 2023-10-01. (21/14006-7, 21/13271-9, 20/14741-6, 21/11162-8)

ROY, SOUMYABRATA; LI, ZHENGYUAN; CHEN, ZHIWEN; MATA, ASTRID CAMPOS; KUMAR, PAWAN; SARMA, SAURAV CH.; TEIXEIRA, IVO F.; SILVA, INGRID F.; GAO, GUANHUI; TARAKINA, NADEZDA V.; et al. Cooperative Copper Single-Atom Catalyst in 2D Carbon Nitride for Enhanced CO₂ Electrolysis to Methane. Advanced Materials, v. 36, n. 13, p. 13-pg., 2024-01-06. (21/12394-0, 21/11162-8, 20/14741-6)

DA SILVA, MARCOS A. R.; SILVA, INGRID F.; XUE, QI; LO, BENEDICT T. W.; TARAKINA, NADEZDA, V; NUNES, BARBARA N.; ADLER, PETER; SAHOO, SUDHIR K.; BAHNEMANN, DETLEF W.; LOPEZ-SALAS, NIEVES; et al. Sustainable oxidation catalysis supported by light: Fe-poly (heptazine imide) as a heterogeneous single-atom photocatalyst. APPLIED CATALYSIS B-ENVIRONMENTAL, v. 304, p. 11-pg., 2022-05-01. (21/11162-8, 20/14741-6)

ROGOLINO, ANDREA; SILVA, INGRID F.; TARAKINA, NADEZDA V.; DA SILVA, MARCOS A. R.; ROCHA, GUILHERME F. S. R.; ANTONIETTI, MARKUS; TEIXEIRA, IVO F.. Modified Poly(Heptazine Imides): Minimizing H2O2 Decomposition to Maximize Oxygen Reduction. ACS APPLIED MATERIALS & INTERFACES, v. 14, n. 44, p. 10-pg., 2022-10-31. (21/11162-8, 20/14741-6, 22/04748-9, 21/13271-9)

OLIVEIRA, WANESSA L.; DA SILVA, MARCOS A. R.; DIAB, GABRIEL ALI ATTA; G FILHO, JOSE BALENA; PASTANA, VITOR G. S.; SILVA, LUANA L. B.; DE OLIVEIRA, EDUARDA FERREIRA; BATISTA, WALKER VINICIUS FERREIRA DO CARMO; DA CRUZ, TAIS DOS SANTOS; MASTELARO, VALMOR ROBERTO; et al. Selective Photocatalytic Benzene Oxidation Using Iron-Carbon Nitride Fragments Functionalized with Cyamelurate-Like Groups. CHEMPHOTOCHEM, v. N/A, p. 12-pg., 2024-11-20. (21/14006-7, 21/12394-0, 20/14741-6, 21/13271-9)

SILVA, INGRID F.; ROY, SOUMYABRATA; KUMAR, PAWAN; CHEN, ZHI WEN; TEIXEIRA, IVO F.; CAMPOS-MATA, ASTRID; ANTONIO, LOUDIANA M.; LADEIRA, LUIZ O.; STUMPF, HUMBERTO O.; SINGH, CHANDRA VEER; et al. Nanoengineered Au-carbon nitride interfaces enhance photocatalytic pure water splitting to hydrogen. JOURNAL OF MATERIALS CHEMISTRY A, v. 11, n. 43, p. 12-pg., 2023-09-20. (21/11162-8, 20/14741-6)

TEIXEIRA, IVO F.; TARAKINA, NADEZDA, V; SILVA, INGRID F.; LOPEZ-SALAS, NIEVES; SAVATEEV, ALEKSANDR; ANTONIETTI, MARKUS. Overcoming Electron Transfer Efficiency Bottlenecks for Hydrogen Production in Highly Crystalline Carbon Nitride-Based Materials. ADVANCED SUSTAINABLE SYSTEMS, v. 6, n. 3, p. 8-pg., 2022-01-13. (20/14741-6, 21/11162-8)

ROCHA, GUILHERME F. S. R.; DA SILVA, MARCOS A. R.; ROGOLINO, ANDREA; DIAB, GABRIEL A. A.; NOLETO, LUIS F. G.; ANTONIETTI, MARKUS; TEIXEIRA, IVO F.. Carbon nitride based materials: more than just a support for single-atom catalysis. CHEMICAL SOCIETY REVIEWS, v. 52, n. 15, p. 56-pg., 2023-07-06. (21/14006-7, 21/11162-8, 22/04748-9, 20/14741-6, 21/13271-9)

DA SILVA, MARCOS A. R.; CUNHA, CARLA S.; SILVA, LUANA L. B.; FARIAS, ISADORA G.; TEIXEIRA, IVO F.. Chlorine-mediated methane activation: an efficient photocatalytic pathway to valuable chemicals. CHEMICAL COMMUNICATIONS, v. N/A, p. 12-pg., 2025-02-03. (21/13271-9, 23/06070-2, 22/13249-6, 20/14741-6, 23/03714-6)

BATISTA, WALKER VINICIUS FERREIRA DO CARMO; DE OLIVEIRA, WANESSA LIMA; DE OLIVEIRA, EDUARDA FERREIRA; CRUZ, TAIS SANTOS; FERRARI, JEFFERSON LUIS; ARCHANJO, BRAULIO SOARES; GRIGOLETTO, SABRINA; FERREIRA, DALVA ESTER DA COSTA; PEREIRA, FABIANO VARGAS; DIAB, GABRIEL ALI ATTA; et al. Ni Single-Atoms Supported on N-Doped Carbon Prepared by Cation Exchange: Ultrafast Catalyst For The Reduction of Nitroarene Compounds Under Ambient Conditions. CHEMCATCHEM, v. 16, n. 18, p. 13-pg., 2024-07-16. (21/14006-7, 21/12394-0, 20/14741-6, 21/13271-9)

DA SILVA, MARCOS AUGUSTO R.; GIL, JESSICA C.; TORRES, JULIANA A.; SILVA, GELSON T. S. T.; FILHO, JOSE BALENA GABRIEL; VICTORIA, HENRIQUE FERNANDES VIEIRA; KRAMBROCK, KLAUS; TEIXEIRA, IVO F.; RIBEIRO, CAUE. Investigating the Metal-TiO₂ Influence for Highly Selective Photocatalytic Oxidation of Methane to Methanol. ACS APPLIED MATERIALS & INTERFACES, v. 16, n. 32, p. 13-pg., 2024-07-23. (21/13271-9, 18/01258-5, 20/14741-6)

DA SILVA, MARCOS A. R.; TARAKINA, NADEZDA V.; FILHO, JOSE B. G.; CUNHA, CARLA S.; ROCHA, GUILHERME F. S. R.; DIAB, GABRIEL A. A.; ANDO, ROMULO AUGUSTO; SAVATEEV, OLEKSANDR; AGIRREZABAL-TELLERIA, IKER; SILVA, INGRID F.; et al. Single-Atoms on Crystalline Carbon Nitrides for Selective C―H Photooxidation: A Bridge to Achieve Homogeneous Pathways in Heterogeneous Materials. Advanced Materials, v. 35, n. 52, p. 13-pg., 2023-11-20. (20/14741-6, 22/16273-5, 21/12394-0, 21/13271-9, 21/11162-8)

BLASKIEVICZ, SIRLON F.; TEIXEIRA, IVO F.; MASCARO, LUCIA H.; CARTA, MARIOLINO; MCKEOWN, NEIL B.; ZHAO, YUANZHU; MARKEN, FRANK. Hydrogen-Mediated Photoelectrocatalysis with Nickel-Modified Poly(Heptazine Imides). ELECTROCATALYSIS, v. 15, n. 1, p. 10-pg., 2023-11-11. (14/50249-8, 17/11986-5, 20/14741-6)

SILVA, INGRID F.; RIOS, REGIANE D. F.; SAVATEEV, OLEKSANDR; TEIXEIRA, IVO F.. Carbon Nitride-Based Nanomaterials as a Sustainable Catalyst for Biodiesel Production. ACS APPLIED NANO MATERIALS, v. 6, n. 11, p. 10-pg., 2023-05-25. (20/14741-6, 21/11162-8)

SILVA, MARCOS A. R. DA; ROCHA, GUILHERME F. S. R.; DIAB, GABRIEL A. A.; CUNHA, CARLA S.; PASTANA, VITOR G. S.; TEIXEIRA, IVO F.. Simple and straightforward method to prepare highly dispersed Ni sites for selective nitrobenzene coupling to Azo/Azoxy compounds. CHEMICAL ENGINEERING JOURNAL, v. 460, p. 10-pg., 2023-02-18. (20/14741-6, 21/11162-8)

TEIXEIRA, IVO F.; TARAKINA, NADEZDA, V; SILVA, INGRID F.; DIAB, GABRIEL ALI ATTA; SALAS, NIEVES LOPEZ; SAVATEEV, ALEKSANDR; ANTONIETTI, MARKUS. Improving hydrogen production for carbon-nitride-based materials: crystallinity, cyanimide groups and alkali metals in solution working synergistically. JOURNAL OF MATERIALS CHEMISTRY A, v. 10, n. 35, p. 6-pg., 2022-08-15. (21/11162-8, 20/14741-6)

BLASKIEVICZ, S. F.; SANTOS, H. L. S.; TEIXEIRA, I. F.; BOTT-NETO, J. L.; FERNANDEZ, P. S.; MASCARO, L. H.. Nickel-modified polymeric carbon nitride for improving TiO2-based photoanode: photoelectrocatalytical evaluation and mechanistical insights. MATERIALS TODAY NANO, v. 18, p. 12-pg., 2022-06-01. (19/07449-0, 18/16401-8, 19/26860-2, 20/14741-6, 17/11986-5, 13/07296-2, 18/20952-0)