Regulating the Local Electronic Structure of Copper Single Atoms with Unsaturated B,O-Coordination for Selective ¹O₂ Generation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12414 - 12424

Published: Sept. 7, 2023

Generating singlet oxygen (1O2) on single atom catalysts (SACs) in peroxymonosulfate (PMS)-based Fenton-like reactions exhibits great potential for selective degradation of contaminants complex wastewater. Clarifying the structure–activity relationship between electronic structure SACs and 1O2 generation selectivity is crucial precise design efficient catalysts, but it challenging. Herein, Cu with different structures (namely, Cu–O2X, where X = N, S, B, P, O) investigated by density functional theory calculations using adsorption terminal atoms PMS as an activity descriptor. Significantly, affected center which electron-depleted Cu-O2B site a higher atoms. Experimentally, moiety superior catalytic activation, showing nearly 100% ciprofloxacin rate 0.2250 min–1, outperforming those other counterparts. The high attributed to asymmetric accelerating faster electron transfer O–O bond stretching, lowering energy barrier key intermediates toward generation. This work provides broader perspective regulating sites at atomic level catalysts.

Language: Английский

---

Coordination engineering in single-site catalysts: General principles, characterizations, and recent advances

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 48 - 85

Published: Sept. 21, 2023

Language: Английский

---

Self-carbon-thermal-reduction strategy for boosting the Fenton-like activity of single Fe-N4 sites by carbon-defect engineering

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 20, 2023

Carbon-defect engineering in metal single-atom catalysts by simple and robust strategy, boosting their catalytic activity, revealing the carbon defect-catalytic activity relationship are meaningful but challenging. Herein, we report a facile self-carbon-thermal-reduction strategy for carbon-defect of single Fe-N4 sites ZnO-Carbon nano-reactor, as efficient catalyst Fenton-like reaction degradation phenol. The vacancies easily constructed adjacent to during synthesis, facilitating formation C-O bonding lowering energy barrier rate-determining-step Consequently, Fe-NCv-900 with exhibits much improved than Fe-NC-900 without abundant vacancies, 13.5 times improvement first-order rate constant phenol degradation. shows high (97% removal ratio only 5 min), good recyclability wide-ranging pH universality (pH range 3-9). This work not provides rational improving catalysts, also deepens fundamental understanding on how periphery environment affects property performance metal-N4 sites.

Language: Английский

---

Acceleration of Fe3+/Fe2+ cycle in garland-like MIL-101(Fe)/MoS2 nanosheets to promote peroxymonosulfate activation for sulfamethoxazole degradation

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 470, P. 144190 - 144190

Published: June 24, 2023

Language: Английский

---

Embedding electronic perpetual motion into single-atom catalysts for persistent Fenton-like reactions

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(4)

Published: Jan. 18, 2024

In our quest to leverage the capabilities of emerging single-atom catalysts (SACs) for wastewater purification, we confronted fundamental challenges related electron scarcity and instability. Through meticulous theoretical calculations, identified optimal placements nitrogen vacancies (Nv) iron (Fe) sites, uncovering a dual-site approach that significantly amplified visible-light absorption charge transfer dynamics. Informed by these computational insights, cleverly integrated Nv into catalyst design boost density around atoms, yielding potent flexible photoactivator benign peracetic acid. This exceptional exhibited remarkable stability effectively degraded various organic contaminants over 20 cycles with self-cleaning properties. Specifically, sites captured electrons, enabling their swift adjacent Fe under visible light irradiation. mechanism accelerated reduction formed "peracetic acid-catalyst" intermediate. Theoretical calculations were used elucidate synergistic interplay dual mechanisms, illuminating increased adsorption activation reactive molecules. Furthermore, pathways on conduction band elaborately explored, unveiling production species enhanced photocatalytic processes. A six-flux model associated parameters also applied precisely optimize process, providing invaluable insights future photocatalyst design. Overall, this study offers molecule-level insight rational robust SACs in photo-Fenton-like system, promising implications treatment other high-value applications.

Language: Английский

---