Recent advances of single-atom catalysts in CO₂conversion

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(7), P. 2759 - 2803

Published: Jan. 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.

Language: Английский

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Cu-based high-entropy two-dimensional oxide as stable and active photothermal catalyst

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

Published: June 1, 2023

Cu-based nanocatalysts are the cornerstone of various industrial catalytic processes. Synergistically strengthening stability and activity is an ongoing challenge. Herein, high-entropy principle applied to modify structure nanocatalysts, a PVP templated method invented for generally synthesizing six-eleven dissimilar elements as two-dimensional (2D) materials. Taking 2D Cu2Zn1Al0.5Ce5Zr0.5Ox example, not only enhances sintering resistance from 400 °C 800 but also improves its CO2 hydrogenation pure CO production rate 417.2 mmol g-1 h-1 at 500 °C, 4 times higher than that reported advanced catalysts. When photothermal hydrogenation, it exhibits record photochemical energy conversion efficiency 36.2%, with generation 248.5 571 L yield under ambient sunlight irradiation. The materials provide new route simultaneously achieve activity, greatly expanding application boundaries catalysis.

Language: Английский

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Synergy of Oxygen Vacancies and Ni⁰ Species to Promote the Stability of a Ni/ZrO₂ Catalyst for Dry Reforming of Methane at Low Temperatures

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6486 - 6496

Published: April 27, 2023

Low-temperature dry reforming of methane (DRM) can avoid the sintering nickel and reduce cost process. However, inefficient activation CO2 oxidization Ni0 hamper catalytic performance Ni-based catalysts at low temperatures. Herein, a Ni/ZrO2 catalyst was prepared used in DRM reaction, which exhibited stable activity temperatures (400, 320 300 °C) for 10 h, with CH4 turnover frequencies 0.26 0.18 s–1 °C, respectively. The presence species oxygen vacancies promotes proved by temperature-programmed oxidation (CO2-TPO). Combined O2 decomposition (O2-TPD), C18O2-DRM, situ X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform (DRIFTS) results, after on site, resultant C would react nearby surface lattice ZrO2, forming CO an vacancy. vacancy more electron transfer promote CO2. This work highlights importance emphasizes key role synergistic effect between enhancing stability over low-temperature reactions.

Language: Английский

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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

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Atomically Thick Oxide Overcoating Stimulates Low-Temperature Reactive Metal–Support Interactions for Enhanced Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6702 - 6709

Published: March 15, 2023

Reactive metal–support interactions (RMSIs) induce the formation of bimetallic alloys and offer an effective way to tune electronic geometric properties metal sites for advanced catalysis. However, RMSIs often require high-temperature reductions (>500 °C), which significantly limits tuning compositional varieties. Here, we report that atomically thick Ga2O3 coating Pd nanoparticles enables initiation at a much lower temperature ∼250 °C. State-of-the-art microscopic in situ spectroscopic studies disclose low-temperature initiate rarely reported Ga-rich PdGa alloy phases, distinct from Pd2Ga phase formed traditional Pd/Ga2O3 catalysts after reduction. In CO2 hydrogenation reaction, phases impressively boost methanol dimethyl ether ∼5 times higher than Pd/Ga2O3. infrared spectroscopy reveals greatly favor formate as well its subsequent hydrogenation, thus leading high productivity.

Language: Английский

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Strained few-layer MoS2 with atomic copper and selectively exposed in-plane sulfur vacancies for CO2 hydrogenation to methanol

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

Published: Sept. 21, 2023

Abstract In-plane sulfur vacancies (Sv) in molybdenum disulfide (MoS 2 ) were newly unveiled for CO hydrogenation to methanol, whereas edge Sv found facilitate methane formation. Thus, selective exposure and activation of basal plane is crucial methanol synthesis. Here, we report a mesoporous silica-encapsulated MoS catalysts with fullerene-like structure atomic copper (Cu / @SiO ). The main approach based on physically constrained topologic conversion dioxide (MoO within silica. spherical curvature enables the generation strain inert plane. More importantly, few-layer can selectively expose in-plane reduce Sv. After promotion by copper, resultant Cu exhibits stable specific yield 6.11 mol MeOH Mo –1 h selectivity 72.5% at 260 °C, much superior its counterparts lacking decoration. reaction mechanism promoting role are investigated in-situ DRIFTS XAS. Theoretical calculations demonstrate that compressive facilitates formation hydrogenation, while tensile accelerates regeneration active sites, rationalizing critical strain.

Language: Английский

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Electronic modulation of a single-atom-based tandem catalyst boosts CO₂ photoreduction to ethanol

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(12), P. 5956 - 5969

Published: Jan. 1, 2023

A single-atom-based tandem photocatalyst (In 2 O 3 /Cu–O ) is fabricated for efficient CO -to-ethanol conversion. The electronic interaction between Cu and In promotes C–C coupling of *CO (on site) *COH Cu–O to form OC–COH species.

Language: Английский

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Superstructure-Assisted Single-Atom Catalysis on Tungsten Carbides for Bifunctional Oxygen Reactions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9124 - 9133

Published: March 22, 2024

Single-atom catalysis (SAC) attracts wide interest for zinc–air batteries that require high-performance bifunctional electrocatalysts oxygen reactions. However, catalyst design is still highly challenging because of the insufficient driving force promoting multiple-electron transfer kinetics. Herein, we report a superstructure-assisted SAC on tungsten carbides evolution and reduction In addition to usual single atomic sites, strikingly, reveal presence ordered Co superstructures in interfacial region with induce internal strain promote catalysis. Theoretical calculations show combined effects from atoms strongly reduce adsorption energy intermediates overpotential both The therefore presented impressive activity an ultralow potential gap 0.623 V delivered high power density 188.5 mW cm–2 assembled batteries. This work opens up new opportunities

Language: Английский

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Nickel-Laden Dendritic Plasmonic Colloidosomes of Black Gold: Forced Plasmon Mediated Photocatalytic CO₂ Hydrogenation

ACS Nano, Journal Year: 2023, Volume and Issue: 17(5), P. 4526 - 4538

Published: Feb. 13, 2023

In this work, we have designed and synthesized nickel-laden dendritic plasmonic colloidosomes of Au (black gold-Ni). The photocatalytic CO2 hydrogenation activities black gold-Ni increased dramatically to the extent that measurable photoactivity was only observed with catalyst, a very high CO production rate (2464 ± 40 mmol gNi–1 h–1) 95% selectivity. Notably, reaction carried out in flow reactor at low temperature atmospheric pressure without external heating. catalyst stable for least 100 h. Ultrafast transient absorption spectroscopy studies indicated indirect hot-electron transfer from gold Ni less than fs, corroborated by reduction Au–plasmon electron–phonon lifetime bleach signal associated d-band filling. Photocatalytic rates on excited showed superlinear power law dependence light intensity, exponent 5.6, while quantum efficiencies an increase intensity temperature, which hot-electron-mediated mechanism. kinetic isotope effect (KIE) (1.91) higher dark (∼1), further electron-driven hydrogenation. Black catalyzed presence electron-accepting molecule, methyl-p-benzoquinone, reduced rate, asserting Operando diffuse reflectance infrared Fourier transform (DRIFTS) took place direct dissociation path via linearly bonded Ni–CO intermediates. outstanding catalytic performance may provide way develop catalysts other processes using gold.

Language: Английский

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Remote Synergy between Heterogeneous Single Atoms and Clusters for Enhanced Oxygen Evolution

Nano Letters, Journal Year: 2023, Volume and Issue: 23(8), P. 3309 - 3316

Published: March 22, 2023

Integrating single atoms and clusters into one system is a novel strategy to achieve desired catalytic performances. Compared with homogeneous single-atom cluster catalysts, heterogeneous ones combine the merits of different species therefore show greater potential. However, it still challenging construct systems species, underlying mechanism for activity improvement remains unclear. In this work, we developed catalyst (ConIr1/N-C) efficient oxygen evolution. The Ir worked in synergy Co at distance about 8 Å, which optimized configuration key intermediates. Consequently, evolution was significantly improved on ConIr1/N-C relative (Con/N-C), exhibiting an overpotential lower by 107 mV than that Con/N-C 10 mA cm-2 turnover frequency 50.9 times as much 300 mV.

Language: Английский

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