Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2

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

Published: Feb. 27, 2023

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for C3H8 prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin layers. promote formation neighbouring oxygen vacancies (VOs) matrix. These modulate electronic coupling interaction between adjacent Ti form a unique Cu-Ti-VO unit A high electron-based selectivity 64.8% (product-based 32.4%), 86.2% total hydrocarbons 50.2%) are achieved. Theoretical calculations suggest that may stabilize key *CHOCO *CH2OCOCO intermediates reduce their energy levels, tuning both C1-C1 C1-C2 couplings thermodynamically-favourable exothermal processes. Tandem catalysis mechanism potential reaction pathway tentatively proposed formation, involving overall (20e- - 20H+) reduction three molecules at room temperature.

Language: Английский

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Integrating Dual-Metal Sites into Covalent Organic Frameworks for Enhanced Photocatalytic CO₂ Reduction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4316 - 4329

Published: March 15, 2023

Photocatalytic CO2 reduction holds great promise for synchronously addressing carbon neutrality and producing fuels, although enhancing the photocatalyst activity tuning product selectivity remain enormous challenges. Herein, we synthesized four crystalline porous benzothiadiazole-based covalent organic frameworks (COFs) with different carbonyl groups reported a dual metalation strategy to fabricate Co Ni dual-metal sites anchored on COFs by interaction between metal thiadiazole high-performance photoreduction. Among as-synthesized metalated Co/Ni sites, CoNi–COF-3 achieved an impressive CO generation rate of 2567 μmol g–1 h–1 92.2%, which were significantly higher than those single sites. Experimental theoretical results revealed that superior photocatalytic performance was attributed synergic effect fully β-ketoenamine-tautomerized COF-3 configuration not only facilitated photogenerated charge carrier dynamics but also reduced energy barriers *COOH formation promoted adsorption desorption. This work provides valuable insights into future design improved COF photocatalysts conversion.

Language: Английский

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Tuning oxygen vacancies in Bi4Ti3O12 nanosheets to boost piezo-photocatalytic activity

Nano Energy, Journal Year: 2023, Volume and Issue: 108, P. 108202 - 108202

Published: Jan. 11, 2023

Piezo-photocatalysis has emerged as a promising strategy to address environmental pollution and the fast-growing energy shortage. Unfortunately, current efficiencies of piezo-photocatalysts are still far from ideal, improving their catalytic efficiency remains challenging. In this paper, we introduce oxygen vacancies (OVs) in Bi4Ti3O12 (BIT) nanosheets boost piezo-photocatalytic performance. Compared pristine BIT nanosheets, with an optimized OV concentration exhibit excellent activity, enhancement 2.2 times degradation rate constant (k = 0.214 min−1) for Rhodamine B (RhB). The effect OVs on adsorption Bader charges was also investigated using density functional theory (DFT) calculations, which shed light underlying mechanism that improves process presence OVs. Specifically, introduction increases charges, resulting charge transfer between O2/H2O BIT, thus facilitating process. This study provides deeper understanding into regulation enhanced activity opens new avenues designing high-performance piezo-photocatalysts.

Language: Английский

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Near-Infrared-Responsive Photocatalytic CO₂ Conversion via In Situ Generated Co₃O₄/Cu₂O

ACS Nano, Journal Year: 2023, Volume and Issue: 17(11), P. 10976 - 10986

Published: May 24, 2023

Photocatalytic CO2 conversion to fuels is a promising strategy for achieving global carbon neutrality. However, infrared light, which accounts ∼50% of the full sunlight spectrum, has not yet been effectively utilized via photocatalysis. Here, we present an approach directly power photocatalytic reduction using near-infrared light. This light-responsive process occurs on in situ generated Co3O4/Cu2O photocatalyst with nanobranch structure. Photoassisted Kelvin probe force microscopy and relative measurements demonstrate increase surface photovoltage after illumination by We also find that Cu(I) this could facilitate formation *CHO intermediate, thus enabling high-performance CH4 production yield 6.5 μmol/h selectivity 99%. Moreover, perform practically oriented direct solar-driven under concentrated achieve fuel 12.5 μmol/h.

Language: Английский

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A novel NiO/BaTiO3 heterojunction for piezocatalytic water purification under ultrasonic vibration

Ultrasonics Sonochemistry, Journal Year: 2022, Volume and Issue: 92, P. 106285 - 106285

Published: Dec. 28, 2022

This work designed and prepared a novel heterojunction composite NiO/BaTiO3 through method of photodeposition used it in piezocatalytic dye removal for the first time. Results test indicated that presented superior efficiency stability RhB degradation under vibration ultrasonic waves. The best sample synthesized light irradiation 2 h displayed an rate 2.41 h-1, which was 6.3 times faster than pure BaTiO3. By optimizing reaction conditions, constant can further reach 4.14 h-1 A variety systematic characterizations were executed to determine reason excellent performance NiO/BaTiO3. band potentials NiO BaTiO3 are found coincide, at their contact interface, they may create type-II p-n structure. Driven by potential difference built-in electric field, piezoelectrically enriched charge carriers migrate between BaTiO3, resulting improved separation increase piezoelectric catalytic performance. study provide catalyst promising idea design highly efficient catalysts field catalysis.

Language: Английский

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Highly Selective Ethylene Production from Solar-Driven CO₂ Reduction on the Bi₂S₃@In₂S₃ Catalyst with In–S_V–Bi Active Sites

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2302 - 2312

Published: Jan. 30, 2023

Photothermal catalysis that utilizes solar energy to not only generate charge carriers but also supply heat input represents a potentially sustainable strategy for the efficient conversion of CO2 valuable chemicals. It is highly desirable develop photothermal catalysts with broadband light absorption across whole spectrum, conversion, and appropriate active sites. In this work, Bi2S3@In2S3 heterostructure catalyst fabricated via one-step solvothermal synthesis, where Bi2S3 serves as material synchronously affords photoexcited carriers. Experimental results indicate photoinduced trigger H2O-assisted reduction elevated temperature kinetically accelerates reaction. Furthermore, tightly bonded heterointerfaces provide unique In–SV–Bi centers consisting adjacent Bi atoms coupled sulfur vacancies, which reduces barriers activation C–C coupling, facilitating generation dimerization CO intermediates selective C2H4 production. The integration sites effect into induces high rate 11.81 μmol gcat–1 h–1 near 90% selectivity under simulated sunlight without extra input. catalytic mechanism expounded by in situ characterizations theoretical calculations. This work would some enlightening guidance construct direct transformation multicarbon (C2+) products energy.

Language: Английский

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Rational design of MoS2@COF hybrid composites promoting C-C coupling for photocatalytic CO2 reduction to ethane

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 325, P. 122393 - 122393

Published: Jan. 9, 2023

Language: Английский

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Catalyzing Artificial Photosynthesis with TiO₂ Heterostructures and Hybrids: Emerging Trends in a Classical yet Contemporary Photocatalyst

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: Oct. 11, 2023

Titanium dioxide (TiO

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Cu-Based Materials for Enhanced C2+ Product Selectivity in Photo-/Electro-Catalytic CO2 Reduction: Challenges and Prospects

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 16(1)

Published: Jan. 4, 2024

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues the energy shortages. Among materials utilized for catalytic reduction of CO

Language: Английский

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Engineering Single Cu Sites into Covalent Organic Framework for Selective Photocatalytic CO₂ Reduction

Small, Journal Year: 2023, Volume and Issue: 19(22)

Published: March 3, 2023

Photocatalytic CO2 conversion into value-added chemicals is a promising route but remains challenging due to poor product selectivity. Covalent organic frameworks (COFs) as an emerging class of porous materials are considered candidates for photocatalysis. Incorporating metallic sites COF successful strategy realize high photocatalytic activities. Herein, 2,2'-bipyridine-based bearing non-noble single Cu fabricated by chelating coordination dipyridyl units reduction. The coordinated not only significantly enhance light harvesting and accelerate electron-hole separation also provide adsorption activation molecules. As proof concept, the Cu-Bpy-COF representative catalyst exhibits superior activity reducing CO CH4 without photosensitizer, impressively, selectivity can be readily modulated changing reaction media. Experimental theoretical results reveal crucial role in promoting photoinduced charge solvent effect regulating selectivity, which provides important sight onto design photocatalysts selective photoreduction.

Language: Английский

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