TY - JOUR
T1 - Sustainable oxidation catalysis supported by light: Fe-poly (heptazine imide) as a heterogeneous single-atom photocatalyst
AU - da Silva, Marcos A.R.
AU - Silva, Ingrid F.
AU - Xue, Qi
AU - Lo, Benedict T.W.
AU - Tarakina, Nadezda V.
AU - Nunes, Barbara N.
AU - Adler, Peter
AU - Sahoo, Sudhir K.
AU - Bahnemann, Detlef W.
AU - López-Salas, Nieves
AU - Savateev, Aleksandr
AU - Ribeiro, Caue
AU - Kühne, Thomas D.
AU - Antonietti, Markus
AU - Teixeira, Ivo F.
N1 - Funding Information:
I.F.T thanks the Alexander von Humboldt Foundation for his postdoctoral fellowship. SKS and TDK acknowledge the generous allocation of computing time by the Paderborn Center for Parallel Computing (PC2) on OCuLUS and the FPGA-based supercomputer NOCTUA. CR and IFT acknowledges CAPES/Alexander von Humboldt Foundation for Experienced Researchers Fellowship : Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-CAPES (88881.145566/2017–1 and 88881.368085/2019-01) and Return Fellowship. This research was supported financially by the Max Planck Society. The authors IFT, MARS and CR are grateful to the Brazilian funding agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-CAPES, Conselho Nacional de Desenvolvimento Científico e Tecnológico-CNPq (423196/2018-9) and Fundação de Amparo à Pesquisa do Estado de São Paulo-FAPESP (2020/14741-6; 2018/012585 and 2021/11162-8) for financial support. BNN gratefully acknowledges the financial support from Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-CAPES, Brazil, from the CAPES/DAAD/CNPQ (15/2017) program, grant number 88887.161403/2017-00. The studies performed in the laboratory “Photoactive nanocompositematerials” were supported by Saint-Petersburg State University (ID:73032813).
Funding Information:
I.F.T thanks the Alexander von Humboldt Foundation for his postdoctoral fellowship. SKS and TDK acknowledge the generous allocation of computing time by the Paderborn Center for Parallel Computing (PC2) on OCuLUS and the FPGA-based supercomputer NOCTUA. CR and IFT acknowledges CAPES/Alexander von Humboldt Foundation for Experienced Researchers Fellowship : Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-CAPES ( 88881.145566/2017–1 and 88881.368085/2019-01 ) and Return Fellowship. This research was supported financially by the Max Planck Society. The authors IFT, MARS and CR are grateful to the Brazilian funding agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior- CAPES , Conselho Nacional de Desenvolvimento Científico e Tecnológico- CNPq ( 423196/2018-9 ) and Fundação de Amparo à Pesquisa do Estado de São Paulo- FAPESP ( 2020/14741-6 ; 2018/012585 and 2021/11162-8 ) for financial support. BNN gratefully acknowledges the financial support from Coordenação de Aperfeiçoamento de Pessoal de Nível Superior-CAPES, Brazil, from the CAPES/DAAD/CNPQ (15/2017) program, grant number 88887.161403/2017-00 . The studies performed in the laboratory “Photoactive nanocompositematerials” were supported by Saint-Petersburg State University (ID: 73032813 ).
Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2022/5
Y1 - 2022/5
N2 - Fe-N-C materials, when prepared as single-atom catalysts (SAC), display excellent activities in oxidation reactions. The systematic investigation of the iron coordination mode revealed that Fe-N4C catalysts are the most active for C-H bond oxidation. However, many of these catalysts are synthesized through pyrolysis, which is characterized by a lack of control and structures with heterogeneous composition, rarely presenting only atomically dispersed Fe−N − C as active sites. Herein, an alternative, reliable and easily reproducible method to obtain highly active Fe SACs (atomically dispersed) with Fe-N4 sites is presented, which is based on ion exchange of sodium from high crystalline sodium poly(heptazine imide) (Na-PHI) by other ions. The obtained catalyst can photocatalytically oxidize C-H bonds selectively toward ketones using only dioxygen. Detailed mechanism investigations indicate that the active species in the C-H bond oxidation are highly valent Fe(IV)/Fe(V)-oxo species, which are further activated by the holes generated at the PHI support under light irradiation.
AB - Fe-N-C materials, when prepared as single-atom catalysts (SAC), display excellent activities in oxidation reactions. The systematic investigation of the iron coordination mode revealed that Fe-N4C catalysts are the most active for C-H bond oxidation. However, many of these catalysts are synthesized through pyrolysis, which is characterized by a lack of control and structures with heterogeneous composition, rarely presenting only atomically dispersed Fe−N − C as active sites. Herein, an alternative, reliable and easily reproducible method to obtain highly active Fe SACs (atomically dispersed) with Fe-N4 sites is presented, which is based on ion exchange of sodium from high crystalline sodium poly(heptazine imide) (Na-PHI) by other ions. The obtained catalyst can photocatalytically oxidize C-H bonds selectively toward ketones using only dioxygen. Detailed mechanism investigations indicate that the active species in the C-H bond oxidation are highly valent Fe(IV)/Fe(V)-oxo species, which are further activated by the holes generated at the PHI support under light irradiation.
KW - Benzene Oxidation
KW - Iron
KW - Photooxidation
KW - Poly (heptazine imide)
KW - Single-atom catalysis
UR - https://www.scopus.com/pages/publications/85120628682
U2 - 10.1016/j.apcatb.2021.120965
DO - 10.1016/j.apcatb.2021.120965
M3 - Journal article
AN - SCOPUS:85120628682
SN - 0926-3373
VL - 304
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 120965
ER -