| Full text | |
| Author(s): Show less - |
Piankova, Diana V.
;
Zschiesche, Hannes
;
Tyutyunnik, Alexander P.
;
Grape, Erik Svensson
;
da Silva, Caio Vinicius C. R.
;
Guimaraes Jr, Walber G.
;
de Moura, Andre. F.
;
Reis, Izadora F.
;
Diab, Gabriel Ali A.
;
Balena Filho, G. Jose
;
Teixeira, Ivo F.
;
Tarakina, Nadezda V.
Total Authors: 12
|
| Document type: | Journal article |
| Source: | ADVANCED FUNCTIONAL MATERIALS; v. N/A, p. 13-pg., 2025-06-20. |
| Abstract | |
Carbon nitrides are among the most efficient and extensively studied transition-metal-free photocatalysts, yet their industrial application is limited by high charge recombination, poor charge transport, and insufficient absorption above 460 nm. This study investigates how fine-tuning the crystal structure of carbon nitrides helps to overcome these challenges and to enhance their photocatalytic performance. We used poly(heptazine imides) (PHIs) with various cations (M = H+, Na+, K+, Mg2(+)) as a model system. Na-PHI exhibits the highest activity among PHIs with monovalent cations, as the combination of solvated Na+ cations and rotational defects, experimentally observed in this study for the first time, optimizes interlayer charge transfer. Greater photocatalytic efficiency observed for Mg-PHI is attributed to the preservation of rotational defects and the higher oxidation state of Mg2(+), which enhances charge density and facilitates charge transfer. Density functional theory (DFT) and spectroscopic analyses reveal that Na-PHI and Mg-PHI share a valence band dominated by nitrogens and a conduction band primarily influenced by carbons, with both cations contributing to n-type doping. Mg-PHI features sub-gap impurity states, reducing the band gap and extending light absorption. Excited-state molecular dynamic simulations further demonstrate that water molecules contribute more significantly to charge transfer. highlighting an additional key factor in optimizing photocatalytic performance. (AU) | |
| FAPESP's process: | 21/12394-0 - Sustainable synthetic methods employing catalysis, benign solvents, safer reagents, and bio-renewable feedstock |
| Grantee: | Arlene Gonçalves Corrêa |
| Support Opportunities: | Research Projects - Thematic Grants |
| FAPESP's process: | 23/10329-1 - Production of value-added organic compounds (C2+) through the dry electrochemical reform of CH4 in supercritical CO2. |
| Grantee: | José Balena Gabriel Filho |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |
| FAPESP's process: | 24/11848-5 - Single Atoms supported on N-doped carbon: A Novel Platform for Single Atom Catalysis |
| Grantee: | Izadora Fonseca Reis |
| Support Opportunities: | Scholarships in Brazil - Support Program for Fixating Young Doctors |
| FAPESP's process: | 21/14006-7 - PHI/PTI-single-atoms controlled synthesis and energy applications |
| Grantee: | Gabriel Ali Atta Diab |
| Support Opportunities: | Scholarships in Brazil - Doctorate (Direct) |
| FAPESP's process: | 21/11162-8 - Multi-user equipment approved in grant 2020/14741-6: GC-MS/FID/TCD (2 injetores+Loop+Sistema valvulado) |
| Grantee: | Ivo Freitas Teixeira |
| Support Opportunities: | Multi-user Equipment Program |
| FAPESP's process: | 20/14741-6 - Graphitic carbon nitrides as platforms for single-atom photocatalysis: moving towards design principles for improved performance |
| Grantee: | Ivo Freitas Teixeira |
| Support Opportunities: | Research Grants - Young Investigators Grants |