Atomically Contacted Cs₃Bi₂Br₉ QDs@UiO‐66 Composite for Photocatalytic CO₂ Reduction

Small, Journal Year: 2024, Volume and Issue: 20(34)

Published: April 9, 2024

Abstract Metal halide perovskite quantum dots (QDs) are widely studied in the field of photocatalytic CO 2 due to their strong light absorption and long carrier migration length. However, it can not exhibit high catalytic performance because radiative recombination lack effective sites. organic frameworks (MOFs) encapsulated QDs only solve aforementioned problems, but also maintain own unique characteristics with ultra‐high specific surfaces area abundant metal In this work, lead‐free bismuth‐based into Zr‐based MOF (UiO‐66), which combines advantages power conversion efficiency surface porosity UiO‐66. addition, benefiting from close contact between Cs 3 Bi Br 9 UiO‐66 enables photogenerated electrons be rapidly transferred MOF. As a result, @UiO‐66 composite exhibits higher yield for reduction than that prepared large‐sized

Language: Английский

---

Deciphering orbital hybridization in heterogeneous catalysis

Electron, Journal Year: 2024, Volume and Issue: 2(1)

Published: Jan. 24, 2024

Abstract The catalytic coordinate is essentially the evolving frontier orbital interaction while feeding with materials and adsorbates under proper reaction conditions. heterogeneous mechanism involves initial adsorption activation of reactants, subsequent intermediate transformation, final target product desorption, regeneration materials. In these processes, modulations in terms hybridization/coupling allow an intrinsic control on both thermodynamics kinetics. Concerned charge transfer redistribution, splitting rearrangement specific orientation, spin change crossover pose a formidable challenge elucidation; it hard to precisely correlate apparent activity selectivity, let alone rational it. Therefore, deciphering couplings inside round highly desirable dependent descriptor further provides in‐depth insights into catalyst design at molecule level. This review hopes provide comprehensive understanding hybridizations, modulations, correlated descriptors catalysis.

Language: Английский

---

Unlocking Spin Gates of Transition Metal Oxides via Strain Stimuli to Augment Potassium Ion Storage

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 8, 2024

Abstract Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost‐effectiveness and a broad potential window. However, their full is limited by poor understanding of slow reaction kinetics stability issues. This study diverges from conventional complex nano‐structuring, concentrating instead on spin‐related charge transfer orbital interactions to enhance the dynamics TMOs during storage processes. We successfully reconfigured degeneracy spin‐dependent electronic occupancy disrupting symmetry magnetic cobalt (Co) sites through straightforward strain stimuli. The this approach lies unfilled Co 3d shell, which serves as regulator for carrier within reaction. observed that opening these ′spin gates′ occurs transition symmetric low‐spin state an asymmetric high‐spin state, resulting enhanced maintained structural stability. Specifically, spin‐rearranged Al−Co 3 O 4 exhibited specific capacitance 1371 F g −1 , 38 % higher than unaltered . These results not only shed light spin effects but also establish new paradigm designing materials with improved efficiency.

Language: Английский

---

Regulating the Oxygen Vacancy on Bi₂MoO₆/Co₃O₄ Core‐Shell Nanocage Enables Highly Selective CO₂ Photoreduction to CH₄

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 6, 2024

Abstract Photocatalytic CO 2 reduction reaction (CO RR) into high‐value‐added fuels has received significant attention, yet multiple electron and proton processes involved in RR result low selectivity. Herein, a strategy involving oxygen vacancies (Ovs)‐enriched Bi MoO 6 coated on ZIF‐67‐derived Co 3 O 4 to construct well‐defined core‐shell nanocage is developed, which drives effective photoconversion CH with nearly 100% selectivity high apparent quantum efficiency of 2.5% at 420 nm pure water under simulated irradiation. Theoretical calculations experiments exhibit that the potential difference stemming from built‐in electric field provides guarantee for occurring H oxidation set . Numerous exposed Ovs formed Bi─O bond by ethylene glycol mediated approach promotes adsorption charge separation efficiency, can optimize kinetics thermodynamics, facilitating hydrogenation key intermediate *CO generate This work new controlled vacancy generation photocatalysts achieve high‐performance methanation.

Language: Английский

---

Artificial photosynthetic system for diluted CO2 reduction in gas-solid phase

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 11, 2024

Rational design of robust photocatalytic systems to direct capture and in-situ convert diluted CO2 from flue gas is a promising but challenging way achieve carbon neutrality. Here, we report new type host-guest photocatalysts by integrating CO2-enriching ionic liquids photoactive metal-organic frameworks PCN-250-Fe2M (M = Fe, Co, Ni, Zn, Mn) for artificial photosynthetic reduction in gas-solid phase. As result, [Emim]BF4(39.3 wt%)@PCN-250-Fe2Co exhibits record high CO2-to-CO rate 313.34 μmol g−1 h−1 under pure atmosphere 153.42 (15%) with about 100% selectivity. In scaled-up experiments 1.0 g catalyst natural sunlight irradiation, the concentration could be significantly decreased below 85% 10%, respectively, indicating its industrial application potential. Further theoretical calculations reveal that not only benefit enrichment, also form synergistic effect Co2+ sites PCN-250-Fe2Co, resulting significant Gibbs energy barrier during rate-determining step conversion. Artificial fuel authors system frameworks, greatly enhancing conversion efficiency.

Language: Английский

---