Efficient Solar‐Driven CO<sub>2</sub> Methanation and Hydrogen Storage Over Nickel Catalyst Derived from Metal–Organic Frameworks with Rich Oxygen Vacancies

Wang, Huiling; Li, Qiang; Chen, Jin; Chen, Jing; Jia, Hongpeng

doi:10.1002/advs.202304406

Cited by 14 publications

(1 citation statement)

References 66 publications

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“…A typical signal similar to stoichiometric ZrO 2 (expected at 182.7 eV) is observed before reduction. The reduced Ni@MOF-545 DS R solid shows a large shift to lower binding energies, down to 181.4 eV for the Zr 3d 5/2 , which is interpreted as emanating from the potential presence of oxygen vacancies in the reduced sample, in line with previous reports. − Interestingly, the larger shift in the DS catalyst than in the IM solid would indicate a larger number of such vacancies. Regarding the C 1s spectral lines (Figure e,f), the XPS shows that the aromatic chemical environment of carbon atoms at 284.1 eV characteristic of the porphyrins is maintained upon reduction of Ni@MOF-545-DS , together with that of the carboxylates at 288.2 eV, supporting our observations from DRIFT (Figure S16) suggesting the integrity of porphyrinic linkers.…”

Section: Resultssupporting

confidence: 89%

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Chen,

Brubach,

Tran

et al. 2024

ACS Appl. Mater. Interfaces

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We report the use of Zr-based metal−organic frameworks (MOFs) as supports to prepare catalysts with uniformly and highly dispersed Ni nanoparticles (NPs) for CO 2 hydrogenation into CH 4 . In the first step, we studied the MOF support under catalytic conditions using operando diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, ex situ characterizations (PXRD, XPS, TEM, and EDX-element mapping), and DFT calculations. We showed that the high-temperature conditions undoubtedly confer a potential for catalytic functionality to the solids toward CH 4 production, while no role of the Cu could be evidenced. The MOF was shown to be transformed into a catalytically active material, amorphized but still structured with dehydroxylated Zr-oxoclusters, in line with DFT calculations. In the second step, Ni@MOF-545 catalysts were prepared using either impregnation (IM) or double solvent (DS) methods, followed by a dry reduction (R) route under H 2 to immobilize Ni NPs. The highest catalytic activity was obtained with the Ni@MOF-545 DS R catalyst (595 mmol CH4 g Ni −1 h −1 ) with 100% CH 4 selectivity and 60% CO 2 conversion after ∼3 h. The higher catalytic activity of Ni@MOF-545 DS R is a result of much smaller (∼5 nm) and better dispersed Ni NPs than in the IM sample (20−40 nm), the latter exhibiting sintering. The advantages of the encapsulation of Ni NPs by the DS method and of the use of a MOF-545-based support are discussed, highlighting the interest of designing yetunexplored Zr-based MOFs loaded with Ni NPs for CO 2 hydrogenation.

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Section: Resultssupporting

confidence: 89%

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Chen,

Brubach,

Tran

et al. 2024

ACS Appl. Mater. Interfaces

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Enhanced Photo‐Thermal CO₂ Methanation with Tunable Ru_xNi_1‐x Catalytic Sites: Alloying Beyond Pure Ru

Guo,

Wang,

Tang

et al. 2024

Adv Funct Materials

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Developing solid‐solution nano‐alloys from immiscible metals has garnered significant interest; however, the high formation entropy poses substantial challenges in synthesis, hindering a comprehensive understanding of the catalytic mechanisms under alloying effects. Herein, the synthesis of small‐sized (≈2.5 nm) RuxNi1‐x solid‐solution alloy nanoparticles with precisely controlled Ru/Ni ratios across a broad compositional range is reported for the first time, despite their bulk immiscibility. The Ru0.76Ni0.24/TiO2 catalyst, with an optimized Ru/Ni ratio, delivers superior photo‐thermal catalytic activity for CO2 methanation, achieving a CH4 production rate of 3.58 mol gmetal−1 h−1 with 94% selectivity at 250 °C under light irradiation, representing a 2.82‐fold enhancement over monometallic Ru/TiO2. Comprehensive investigations reveal that the reconstruction of electronic structure at Ru–Ni active sites enhances the adsorption/activation of reactants, promotes the transformation of intermediate HCO3* to HCOO*, and facilitates the separation of the photo‐generated charge carriers witnessed by the femtosecond time‐resolved transient absorption (fs‐TA) spectroscopy. These combined effects collectively result in significantly enhanced CH4 formation performance. This work highlights the potential of regulating catalytic sites in immiscible metal combinations for photo‐thermal catalytic CO2 conversion, underscoring the promise of these cost‐effective alloys in heterogeneous catalysis.

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RuCo/ZrO₂ Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO₂ Methanation

Yang,

Liu,

Xing

et al. 2024

Advanced Science

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Photothermal CO2 methanation reaction represents a promising strategy for addressing CO2‐related environmental issues. The presence of efficient tandem catalytic sites with a localized high‐temperature is an effective pathway to enhance the performance of CO2 methanation. Here the bimetallic RuCo nanoparticles anchored on ZrO2 fiber cotton (RuCo/ZrO2) as a photothermal catalyst for CO2 methanation are prepared. A significant photothermal CO2 methanation performance with optimal CH4 selectivity (99%) and rate (169.93 mmol gcat−1 h−1) is achieved. The photothermal energy of the RuCo bimetallic nanoparticles, confined by the infrared insulation and low thermal conductivity of the ZrO2 fiber cotton (ZrO2 FC), provides a localized high‐temperature. In situ spectroscopic experiments on RuCo/ZrO2, Ru/ZrO2, and Co/ZrO2 indicate that the construction of tandem catalytic sites, where the Co site favors CO2 conversion to CO while incorporating Ru enhances CO* adsorption for subsequent hydrogenation, results in a higher selectivity toward CH4. This work opens a new insight into designing tandem catalysts with a photothermal confinement effect in CO2 methanation reaction.

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Efficient Solar‐Driven CO₂ Methanation and Hydrogen Storage Over Nickel Catalyst Derived from Metal–Organic Frameworks with Rich Oxygen Vacancies

Cited by 14 publications

References 66 publications

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Enhanced Photo‐Thermal CO₂ Methanation with Tunable Ru_xNi_1‐x Catalytic Sites: Alloying Beyond Pure Ru

RuCo/ZrO₂ Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO₂ Methanation

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Efficient Solar‐Driven CO2 Methanation and Hydrogen Storage Over Nickel Catalyst Derived from Metal–Organic Frameworks with Rich Oxygen Vacancies

Cited by 14 publications

References 66 publications

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO2 Methanation

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO2 Methanation

Enhanced Photo‐Thermal CO2 Methanation with Tunable RuxNi1‐x Catalytic Sites: Alloying Beyond Pure Ru

RuCo/ZrO2 Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO2 Methanation

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Product

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Efficient Solar‐Driven CO₂ Methanation and Hydrogen Storage Over Nickel Catalyst Derived from Metal–Organic Frameworks with Rich Oxygen Vacancies

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Zr-Based MOF-545 Metal–Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

Enhanced Photo‐Thermal CO₂ Methanation with Tunable Ru_xNi_1‐x Catalytic Sites: Alloying Beyond Pure Ru

RuCo/ZrO₂ Tandem Catalysts with Photothermal Confinement Effect for Enhanced CO₂ Methanation