Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Environmental Science & Technology, Год журнала: 2023, Номер 57(37), С. 14046 - 14057

Опубликована: Сен. 2, 2023

Precisely identifying the atomic structures in single-atom sites and establishing authentic structure-activity relationships for catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted underlying catalytic activity of Fe-NxC4-x with diverse first-shell environments. Substituting N C to coordinate central Fe atom induces an inferior Fenton-like efficiency. Then, Fe-SACs carrying three configurations (Fe-N2C2, Fe-N3C1, Fe-N4) fabricate facilely demonstrate that optimized environments significantly promote activity. Specifically, reaction rate constant increases from 0.064 0.318 min-1 as number Fe-N 2 4, slightly influencing nonradical mechanism dominated by 1O2. In-depth unveil modulated Fe-N2C2 Fe-N4 optimize d-band electronic regulate binding strength peroxymonosulfate on sites, resulting a reduced energy barrier enhanced The stability actual hospital sewage treatment capacity also showed strong dependency. This strategy local engineering offers vivid example modulating SACs well-regulated environments, ultimately maximizing their

Язык: Английский

---

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

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 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.

Язык: Английский

---

Local Electronic Structure Modulation of Interfacial Oxygen Vacancies Promotes the Oxygen Activation Capacity of Pt/Ce_1–xM_xO_2−δ

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5936 - 5948

Опубликована: Апрель 3, 2024

The asymmetric oxygen vacancies on the surface of doped oxides and at interface between metal oxide are commonly regarded as real active sites for molecular activation reaction, owing to their unique electronic perturbation properties. However, essential rules modulating local structure promote capacity still ambiguous. In this work, a series interfacial vacancy sites, Pt/Ce–Ov–M (Ov, vacancy, M = Y, La, Pr, Nd), with different coordination environments were constructed based Pt/Ce0.95M0.05O2−δ materials. experimental data theoretical calculation results prove that site can capture electrons from Pt d-bands d- f-bands, acting an electron enrichment center. elevated d-band center upward Fermi level significantly boost transfer unoccupied π2p* orbital O2, achieving O2 through π-electron feedback mechanism. Remarkably, Pt/Ce–Ov–Y in Pt/Ce0.95Y0.05O2−δ highest delocalized density exhibited best behaviors catalytic activity aerobic oxidation 5-hydroxymethylfurfural. This work reveals over metal-oxide catalysts is highly dependent d/f-orbital valence-electron modulation, providing more insights into effect vacancy-localized performance.

Язык: Английский

---

Promoting Electroreduction of CO₂ and NO₃⁻ to Urea via Tandem Catalysis of Zn Single Atoms and In₂O_3‐x

Advanced Energy Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 16, 2024

Abstract Urea electrosynthesis from co‐electrolysis of CO 2 and NO 3 − (UECN) offers an innovative route for converting waste /NO into valuable urea. Herein, Zn single atoms anchored on oxygen vacancy (OV)‐rich In O 3‐x (Zn 1 /In ) are developed as a highly active selective UECN catalyst, delivering the highest urea yield rate 41.6 mmol h −1 g urea‐Faradaic efficiency 55.8% at −0.7 V in flow cell, superior to most previously reported catalysts. situ spectroscopic measurements theoretical calculations unveil synergy In/Zn sites OVs promoting process via tandem catalysis mechanism, where ‐OV site activates form * NH while In‐OV CO. The formed spontaneously migrates nearby then couples with generate CONH which is ultimately converted

Язык: Английский

---

Anchored Cobalt Nanoparticles on Layered Perovskites for Rapid Peroxymonosulfate Activation in Antibiotic Degradation

Advanced Materials, Год журнала: 2024, Номер 36(27)

Опубликована: Апрель 16, 2024

Abstract In the Fenton‐like reaction, revealing dynamic evolution of active sites is crucial to achieve activity improvement and stability catalyst. This study reports a perovskite oxide in which atomic (Co 0 ) situ embedded exsolution occurs during high‐temperature phase transition. unique anchoring strategy significantly improves Co 3+ /Co 2+ cycling efficiency at interface inhibits metal leaching peroxymonosulfate (PMS) activation. The Co@L‐PBMC catalyst exhibits superior PMS activation ability could 99% degradation tetracycline within 5 min. combination experimental characterization density functional theory (DFT) calculations elucidates that electron‐deficient oxygen vacancy accepts an electron from 3d‐orbital, resulting significant delocalization site, thereby facilitating adsorption *HSO /*OH intermediate onto “metal‐V O bridge” structure. work provides insights into mechanism level, will guide rational design next‐generation catalysts for environmental remediation.

Язык: Английский

---

Long-range interactions driving neighboring Fe–N4 sites in Fenton-like reactions for sustainable water decontamination

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 5, 2024

Язык: Английский

---

Molecular level removal of antibiotic resistant bacteria and genes: A review of interfacial chemical in advanced oxidation processes

Water Research, Год журнала: 2024, Номер 254, С. 121373 - 121373

Опубликована: Фев. 23, 2024

Язык: Английский

---

Facile synthesis of N-doped carbon nanorods for antibiotics degradation via PMS activation: Mechanism insight and biotoxicity assessment

Separation and Purification Technology, Год журнала: 2024, Номер 340, С. 126849 - 126849

Опубликована: Фев. 20, 2024

Язык: Английский

---

Revealing the Role of Binary Distortion in PMS Activation over Spinel toward Efficient New Pollutants Removal

Advanced Functional Materials, Год журнала: 2024, Номер 34(25)

Опубликована: Фев. 16, 2024

Abstract Improving peroxymonosulfate (PMS) activation efficiency to enhance simultaneous generation of radicals and non‐radicals is essential for removing new pollutants (NPs) in complex waters. However, achieving this with standard lattice‐structured heterogeneous catalysts remains challenging due inefficient electron transfer. Here, CuCo 2 O 4 properties are successfully tuned by controlling lattice distortion, enabling PMS oxidation reduction. Unlike the slow rate transfer metal structures, highly active binary distortion alters structure distribution, exposes more Cu Co sites, lowers adsorption barriers, realizes synergistic production SO •− /•OH), 1 . The k‐value ciprofloxacin as high 17.83 min −1 M , 29.42 times higher than that non‐binary distortion. Additionally, developed intermittent reactor consistently maintains a removal above 95% over five cycles actual wastewater treatment scenarios. This work provides avenue water bodies.

Язык: Английский

---

Construction of Co‐Se‐W at Interfaces of Phase‐Mixed Cobalt Selenide via Spontaneous Phase Transition for Platinum‐Like Hydrogen Evolution Activity and Long‐Term Durability in Alkaline and Acidic Media

Advanced Materials, Год журнала: 2024, Номер 36(28)

Опубликована: Апрель 24, 2024

Abstract Cost‐effective transition metal chalcogenides are highly promising electrocatalysts for both alkaline and acidic hydrogen evolution reactions (HER). However, unsatisfactory HER kinetics stability have severely hindered their applications in industrial water electrolysis. Herein, a nanoflowers‐shaped W‐doped cubic/orthorhombic phase‐mixed CoSe 2 catalyst ((c/o)‐CoSe ‐W) is reported. The W doping induces spontaneous phase from stable cubic (c‐CoSe ) to metastable orthorhombic , which not only enables precise regulation of the ratio two phases but also realizes at interfaces phases. (c/o)‐CoSe ‐W exhibits Pt‐like activity media, with record‐low overpotentials 29.8 mV (alkaline) 35.9 (acidic) 10 mA cm −2 respectively, surpassing vast majority previously reported non‐precious HER. activities originate formation Co–Se–W active species on c‐CoSe side interface, effectively modulates electron structures sites, enhancing H O adsorption dissociation Co sites optimizing * Δ G H* ≈ 0 sites. Benefiting abundant interfaces, displays outstanding long‐term durability media.

Язык: Английский

---