Marriage of Ultralow Platinum and Single-Atom MnN₄ Moiety for Augmented ORR and HER Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(6), С. 4012 - 4020

Опубликована: Март 8, 2023

Hitherto, Pt-based catalysts still are state of the art for oxygen reduction reaction (ORR) and hydrogen evolution (HER), but high dosage, low atom-utilization efficiency, uncontrollable size Pt species seriously impede their applications. Given this, we propose an effective way by enhancing Pt–transition metal single-atom interaction. Due to strong interaction between Mn sites in Mn–N–C species, overgrowth is effectively limited with average smaller than 2.5 nm. Meanwhile, regulated electronic structure drives electron transfer from adjacent sites, endowing reduced energy barrier higher intrinsic activity. As expected, obtained Pt@Mn-SAs/N-C nanocatalyst ideal ultralow loading (1.98 wt %) exhibits extraordinarily ORR mass activity at 0.9 V acidic alkaline media, which 11.1 14.7 times larger that commercial Pt/C, respectively. Moreover, 30 mV, its HER even 33.4 18.7 Pt/C. Theory calculation results show favorable charge density rearrangement resulting electron-enriched negatively shifted d-band centers, weaken surface adsorption key intermediates, boosting ORR/HER This work provides enlightenment integration multiple active centers catalysts.

Язык: Английский

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Enabling Internal Electric Fields to Enhance Energy and Environmental Catalysis

Advanced Energy Materials, Год журнала: 2023, Номер 13(11)

Опубликована: Янв. 29, 2023

Abstract Recent years have witnessed an upsurge of interest in exploiting advanced photo‐/electrocatalysts for efficient energy conversion and environmental remediation. Constructing internal electric fields has been highlighted as a rising star to help facilitate various catalytic processes, with the merits promoting charge transfer/separation, optimizing redox potential creating effective active/adsorption sites. Internal are usually formed by polarization uneven distributions between different constituent layers, which widely exist piezoelectrics, polar surface terminations, heterostructure materials. Herein, groundbreaking interdisciplinary overview latest advances construction improve photo(electro)catalytic electrocatalytic activity is provided. This critical review begins encyclopedic summary classification, advantages, synthesis strategies fields. Subsequently, identification methods thoroughly discussed based on characterization techniques, experiments, theoretical calculations, can provide profound guidance in‐depth study To elaborate theory–structure–activity relationships fields, corresponding reaction mechanisms, modification strategies, performance jointly discussed, along discussion their practical applications. Finally, insightful analysis challenges future prospects field‐based catalysts discussed.

Язык: Английский

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Robust construction of CdSe nanorods@Ti3C2 MXene nanosheet for superior photocatalytic H2 evolution

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 328, С. 122537 - 122537

Опубликована: Фев. 26, 2023

Язык: Английский

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Unraveling the Transformation from Type-II to Z-Scheme in Perovskite-Based Heterostructures for Enhanced Photocatalytic CO₂ Reduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3303 - 3314

Опубликована: Янв. 25, 2024

The ability to create perovskite-based heterostructures with desirable charge transfer characteristics represents an important endeavor render a set of perovskite materials and devices tunable optoelectronic properties. However, due similar material selection band alignment in type-II Z-scheme heterostructures, it remains challenging obtain favorable electron pathway for photocatalysis. Herein, we report robust tailoring effective via transformation highly efficient selective photocatalytic CO2 reduction. Specifically, CsPbBr3/TiO2 CsPbBr3/Au/TiO2 are synthesized then investigated by ultrafast spectroscopy. Moreover, taking as examples, operando experiments theoretical calculations confirm that the heterostructure could be readily transformed into through establishing low-resistance Ohmic contact, which indicates fast is crucial construction, further demonstrated CsPbBr3/Ag/TiO2 CsPbBr3/MoS2 heterostructures. In contrast pristine CsPbBr3 CsPbBr3/TiO2, exhibits 5.4- 3.0-fold enhancement consumption rate DFT situ diffuse reflectance infrared Fourier transform spectroscopy unveil superior CO selectivity attributed lower energy *CO desorption than hydrogenation *HCO. This meticulous design sheds light on modification multifunctional enlightens conscious optimization semiconductor-based catalysis applications.

Язык: Английский

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Highly Selective Photoconversion of CO₂ to CH₄ over SnO₂/Cs₃Bi₂Br₉ Heterojunctions Assisted by S-Scheme Charge Separation

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12623 - 12633

Опубликована: Сен. 13, 2023

Exploring photocatalysts to promote the conversion of CO2 valuable chemical fuels is a highly promising approach for mitigating energy scarcity and environmental pollution. Lead-free perovskite Cs3Bi2Br9 quantum dots (QDs) have attracted considerable attention in photoreduction due robust reduction capability controllable product selectivity. Nevertheless, their potential has been impeded by rapid recombination charge carriers, leading unsatisfactory photocatalytic efficiency. Here, unique SnO2/Cs3Bi2Br9 S-scheme heterojunctions are constructed electrostatically self-assembling SnO2 nanofibers with QDs enhance performance. Density functional theory calculations, along experimental studies, reveal that electrons transfer from SnO2, creating directed interfacial electric field bending bands at interfaces. This facilitates transport photoelectrons Cs3Bi2Br9, forming enabling effective separation powerful photoexcited electron/hole pairs. Additionally, profiting enhanced light absorption contributed narrow-bandgap lower barrier CH4 production over surface, heterostructures unveil superior activities high selectivity 70%, without assistance any molecular catalyst or scavenger.

Язык: Английский

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Stabilization and Performance Enhancement Strategies for Halide Perovskite Photocatalysts

Advanced Materials, Год журнала: 2022, Номер 35(6)

Опубликована: Июль 28, 2022

Abstract Solar‐energy‐powered photocatalytic fuel production and chemical synthesis are widely recognized as viable technological solutions for a sustainable energy future. However, the requirement of high‐performance photocatalysts is major bottleneck. Halide perovskites, category diversified semiconductor materials with suitable energy‐band‐enabled high‐light‐utilization efficiencies, exceptionally long charge‐carrier‐diffusion‐length‐facilitated charge transport, readily tailorable compositional, structural, morphological properties, have emerged new class efficient hydrogen evolution, CO 2 reduction, various organic reactions. Despite noticeable progress, development halide perovskite (HPPs) still hindered by several key challenges: strong ionic nature high hydrolysis tendency induce instability an unsatisfactory activity due to need coactive component realize redox processes. Herein, recently developed advanced strategies enhance stability HPPs comprehensively reviewed. The applicable enhancement first articulated, improvement then explored. Finally, challenges future perspectives associated application in fuels value‐added chemicals presented, indicating irreplaceable role field photocatalysis.

Язык: Английский

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Covalent‐Bonding Oxidation Group and Titanium Cluster to Synthesize a Porous Crystalline Catalyst for Selective Photo‐Oxidation Biomass Valorization

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(37)

Опубликована: Июль 19, 2022

The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti6 -NH2 and benzotrithiophene tricarbaldehyde (BTT). integration them endows with visible-light-adsorption region, effective electron-hole separation-efficiency suitable ability. Specifically, photo-selectivity for HMF-to-FDCA can be >95 % ≈100 conversion, which more than 2, 5, 10 times higher MOF-901 (43 %), (19 %) under-darkness (9 respectively. Notably, an O2 -based mechanism proposed vital roles BTT are verified by DFT calculations. This work might facilitate exploration porous-crystalline-catalysts biomass-valorization.

Язык: Английский

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Metal halide perovskite materials in photocatalysis: Design strategies and applications

Coordination Chemistry Reviews, Год журнала: 2023, Номер 481, С. 215031 - 215031

Опубликована: Фев. 13, 2023

Язык: Английский

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Highly exposed active sites of Au nanoclusters for photocatalytic CO2 reduction

Chemical Engineering Journal, Год журнала: 2022, Номер 451, С. 138392 - 138392

Опубликована: Авг. 2, 2022

Язык: Английский

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Detecting and Quantifying Wavelength‐Dependent Electrons Transfer in Heterostructure Catalyst via In Situ Irradiation XPS

Advanced Science, Год журнала: 2022, Номер 10(4)

Опубликована: Ноя. 14, 2022

The identity of charge transfer process at the heterogeneous interface plays an important role in improving stability, activity, and selectivity heterojunction catalysts. And, situ irradiation X-ray photoelectron spectroscopy (XPS) coupled with UV light optical fiber measurement setup is developed to monitor observe between heterojunction. However, in-depth relationship binding energy wavelength missing based on fact that incident formed by coupling different wavelengths. Furthermore, a quantitative understanding numbers remains elusive. Herein, g-C3 N4 /SnO2 model catalyst, wavelength-dependent Boltzmann function describe changes through utilizing continuously adjustable monochromatic XPS technique established. Using this method, study further reveals electrons number can be readily calculated forming asymptotic model. This methodology provides blueprint for deep charge-transfer rules facilitates future development highly active advanced

Язык: Английский

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