Engineering Single-Atom Active Sites on Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(37), С. 17097 - 17109

Опубликована: Сен. 6, 2022

Solar carbon dioxide (CO2) conversion is an emerging solution to meet the challenges of sustainable energy systems and environmental/climate concerns. However, construction isolated active sites not only influences catalytic activity but also limits understanding structure-catalyst relationship CO2 reduction. Herein, we develop a universal synthetic protocol fabricate different single-atom metal (e.g., Fe, Co, Ni, Zn, Cu, Mn, Ru) anchored on triazine-based covalent organic framework (SAS/Tr-COF) backbone with bridging structure metal-nitrogen-chlorine for high-performance Remarkably, as-synthesized Fe SAS/Tr-COF as representative catalyst achieved impressive CO generation rate high 980.3 μmol g-1 h-1 selectivity 96.4%, over approximately 26 times higher than that pristine Tr-COF under visible light irradiation. From X-ray absorption fine analysis density functional theory calculations, superior photocatalytic performance attributed synergic effect atomically dispersed host, decreasing reaction barriers formation *COOH intermediates promoting adsorption activation well desorption. This work affords rational design state-of-the-art catalysts at molecular level provides in-depth insights efficient conversion.

Язык: Английский

---

Designing covalent organic frameworks with Co-O4 atomic sites for efficient CO2 photoreduction

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

Опубликована: Фев. 28, 2023

Abstract Cobalt coordinated covalent organic frameworks have attracted increasing interest in the field of CO 2 photoreduction to CO, owing their high electron affinity and predesigned structures. However, achieving conversion efficiency is challenging since most Co related coordination environments facilitate fast recombination photogenerated electron-hole pairs. Here, we design two kinds Co-COF catalysts with oxygen atoms find that after tuning environment, reported framework catalyst Co-O 4 sites exhibits a production rate 18000 µmol g −1 h selectivity as 95.7% under visible light irradiation. From in/ex-situ spectral characterizations theoretical calculations, it revealed significantly carrier migration matrixes inhibit pairs photocatalytic process. This work opens way for high-performance photoreduction.

Язык: Английский

---

Porous organic polymers for CO₂capture, separation and conversion

Chemical Society Reviews, Год журнала: 2022, Номер 51(23), С. 9831 - 9852

Опубликована: Янв. 1, 2022

Porous organic polymers (POPs) have long been considered as prime candidates for carbon dioxide (CO2) capture, separation, and conversion. Especially their permanent porosity, structural tunability, stability relatively low cost are key factors in such considerations. Whereas heteratom-rich microporous networks well amine impregnation/functionalization actively exploited to boost the CO2 affinity of POPs, recently, focus has shifted engineering pore environment, resulting a new generation highly POPs rich heteroatoms featuring abundant catalytic sites capture conversion into value-added products. In this review, we aim provide insights structure-property relationships governing using highlight recent advances field.

Язык: Английский

---

Breaking the Scaling Relationship Limit: From Single-Atom to Dual-Atom Catalysts

Accounts of Materials Research, Год журнала: 2022, Номер 3(6), С. 584 - 596

Опубликована: Май 17, 2022

ConspectusRecent decades have witnessed the rapid development of catalytic science, especially after Taylor and Armstrong proposed notion "active site" in 1925. By optimizing reaction paths reducing activation energies reactions, catalysts appear more than 90% chemical production involving homogeneous catalysis, heterogeneous enzyme catalysis. Because 100% efficiency active atom utilization adjustable microenvironment metal centers, single-atom (SACs) shine various fields for enhancing rate, conversion, selectivity reactions. Nevertheless, a solo site determines fixed adsorption mode, intermediates from multistep reactions linking with are related to each other. For specific reaction, it is almost impossible optimally adjust every intermediate on simultaneously. This phenomenon termed scaling relationship limit (SRL) an unavoidable obstacle pure SACs.Dual-atom (DACs), perfectly inheriting advantages SACs, can exhibit better performance simple SACs thus gradually gained researchers' attention. Depending dual-metal structure, sites (DMSs) DACs be divided into two separated heterometal sites, linked homometal sites. Two prescribe distance between electron interaction. Currently, origins summarized following three points: (1) electronic effect, which only one center serves as other plays regulatory role; (2) synergistic centers separately catalyze different core steps improve together; (3) offering additional changes structures break SRL based SACs. Among origins, structure upon DMSs most effective technologies boost property basis To date, few contributions focused catalysis environments, including O2 reduction evolution H2 CO2 N2 conversion reactions.In this Account, summary recent progress regarding will presented. First, unpopular discovery research hot spot illustrated through timeline. In next section, categories, potential revealed by comparison addition, techniques constructing systematically summarized, preparation carbonous, pyrolysis-free, noncarbon-supported, complex-type DACs. Furthermore, underlying energy- environment-related introduced detail assistance theoretical calculations. Finally, we affirm contribution particularly electrocatalysis, provide outlook direction discussing major challenges. It anticipated that Account inspire researchers propel advance

Язык: Английский

---

Covalent organic frameworks towards photocatalytic applications: Design principles, achievements, and opportunities

Coordination Chemistry Reviews, Год журнала: 2022, Номер 475, С. 214882 - 214882

Опубликована: Окт. 14, 2022

Язык: Английский

---

Phosphorus Tailors thed‐Band Center of Copper Atomic Sites for Efficient CO₂Photoreduction under Visible‐Light Irradiation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Июль 8, 2022

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN P3 were fabricated via selective phosphidation, tested visible light-driven reduction by H2 O without sacrificial agents. was exclusively active for CO production a rate 49.8 μmolCO gcat-1 h-1 , outperforming most polymeric (C3 N4 ) based catalysts, while preferably yielded . Experimental theoretical analysis suggested that doping P C3 replacing corner C atom upshifted the d-band center close to Fermi level, which boosted adsorption activation on making efficiently convert CO. In contrast, much lower 3d electron energy exhibited negligible adsorption, thereby preferring formation photocatalytic splitting.

Язык: Английский

---

Recent advances of single-atom catalysts in CO₂conversion

Energy & Environmental Science, Год журнала: 2023, Номер 16(7), С. 2759 - 2803

Опубликована: Янв. 1, 2023

The catalytic transformation of CO 2 into valuable fuels/chemicals is a promising and economically profitable process because it offers an alternative toward fossil feedstocks the benefit transforming cycling on scale-up.

Язык: Английский

---

Microenvironments Enabled by Covalent Organic Framework Linkages for Modulating Active Metal Species in Photocatalytic CO₂ Reduction

Advanced Functional Materials, Год журнала: 2022, Номер 32(17)

Опубликована: Янв. 15, 2022

Abstract Covalent organic frameworks (COFs) are promising platforms for understanding photocatalytic CO 2 reduction processes owing to their predesignable structures and tailor‐made functions. Herein, a nickel‐modified COF composed of N ‐acylhydrazone‐linked electron‐donor electron‐acceptor dyads (H‐COF‐Ni) is reported. H‐COF‐Ni generates 5694 µ mol g −1 with 96% selectivity over H evolution in h under visible light irradiation, which greatly outperforms that typical imine‐linked counterpart. Experimental theoretical results have demonstrated metal active sites host deprived by 2,2′‐bipyridine additive form new catalytic species, the separation transfer process photogenerated charge carriers not main reason activity difference. The linkage‐dependent activation molecules on Ni centers responsible high efficiency. This study provides protocols improve photoreduction performance through modification linkage microenvironments.

Язык: Английский

---

Recent Advances on Single‐Atom Catalysts for CO₂ Reduction

Small Structures, Год журнала: 2022, Номер 4(3)

Опубликована: Окт. 27, 2022

Continuous consumption of fossil energy and excessive CO 2 emission severely restrict human society. Sustainable carbon cycle is a promising technology to simultaneously relieve greenhouse effect crisis based on electrocatalysis photocatalysis. However, the conversion efficiency confined by poor carriers utilization insufficient reactive sites. Single‐atom catalysts (SACs) display outstanding performance in effectively overcoming aforementioned problems. Herein, recent advances SACs for enhancing efficiency, selectivity, long‐range stability reduction are provided. First, characteristics have been introduced detail provide rational design relationship between structure performance, including type, structure, synthesis SACs. Then, high electrocatalytic, photocatalytic, thermocatalytic has discussed disclosing reaction mechanism, such as charge transfer, activation barriers, pathway. In particular, strategies summarized deep insight into designing developing more efficient Finally, an outlook current challenges perspectives proposed. This review aims systematic reference advanced catalytic conversion.

Язык: Английский

---

Configuration of hetero-framework via integrating MOF and triazine-containing COF for charge-transfer promotion in photocatalytic CO2 reduction

Chemical Engineering Journal, Год журнала: 2022, Номер 446, С. 137011 - 137011

Опубликована: Май 14, 2022

Язык: Английский

---