Metal–organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO<sub>2</sub>: the role of the morphology effect

Wang, Mang; Liu, Jinxuan; Guo, Cheng; Gao, Xiaosu; Gong, Chenghuan; Wang, Yan; Liu, Bo; Li, Xiaoxin; Gurzadyan, Gagik G.; Sun, Licheng

doi:10.1039/c8ta00154e

Cited by 270 publications

(150 citation statements)

References 33 publications

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“…Figure 3a indicates that the fluorescence intensity of [Ru(bpy) 3 ]Cl 2 gradually decreases with the increase of the amount of catalyst BIF-29, while the UV/Vis spectrum of photosensitizer remains unchanged by the addition of BIF-29, indicating the luminescence quenching of [Ru(bpy) 3 ]Cl 2 is mainly attributed to the electron transfer from the excited [Ru-(bpy) 3 ]Cl 2 to BIF-29 ( Figure S12a). [16] By contrast, the PL of photosensitizer is not quenched by TEOA( Figure S12b). Thus,t he excited photosensitizer is quenched by BIF-29 via an oxidative quenching.…”

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confidence: 97%

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Zhang

Hong

et al. 2019

Angewandte Chemie

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Photocatalytic reduction of CO 2 to value-added fuel has been considered to be apromising strategy to reduce global warming and shortage of energy.Rational design and synthesis of catalysts to maximumly expose the active sites is the key to activate CO 2 molecules and determine the reaction selectivity. Herein, we synthesizeawell-defined copper-based boron imidazolate cage (BIF-29) with six exposed mononuclear copper centers for the photocatalytic reduction of CO 2 . Theoretical calculations show as ingle Cu site including weak coordinated water delivers anew state in the conduction band near the Fermi level and stabilizes the *COOH intermediate. Steady-state and time-resolved fluorescence spectra showthese Cu sites promote the separation of electron-hole pairs and electron transfer.A saresult, the cage achieves solar-driven reduction of CO 2 to CO with an evolution rate of 3334 mmol g À1 h À1 and ahigh selectivity of 82.6 %.With the development of human activities,t he excessive emission of carbon dioxide (CO 2 )r esults in an increasingly serious environmental problem. To address this issue,o ne of the most promising solutions is direct photochemical reduction of CO 2 to useful chemicals or fuels such as methane, methanol, carbon monoxide,and formic acid. [1] Among these possible target products,the two-electron reduction of CO 2 to CO is al ess hindered process and plays an important role in the chemical industry. [1a,2] To date,m uch research has been devoted to developing selective catalysts for reduction of CO 2 to CO. [3] Precious metals have been identified as promising candidates for CO 2 reduction to CO but their practical applications are still limited. Copper as an earth-abundant metal is ac ritical metal in photosynthesis [4] and Cu-based materials have been regarded as promising catalysts for efficiently photo-or electro-catalyzing CO 2 reduction. [5] To date,v arious Cu-based catalysts have been developed but limited product selectivity due to the presence of multiple neighboring sites for involving CO 2 reduction. To enhance product selectivity,aconventional approach is to tailor the number of nearest neighboring accessible Cu atoms,s uch as reducing the particle size [6] or hybridizing Cu with other metals. [7] Besides these,i ntroducing single active site in ac atalyst has been proven to be an effective strategy to study the reactive pathway and enhance the activity for CO 2 reduction reaction (CO2RR). [8] In particular,t he presence of unsaturated coordinated single active sites or defect can modify the electron structure of catalysts,w hich could stabilize the reaction intermediates and thus depress the energy barrier of the photoreduction CO 2 . [9] Recent studies demonstrate that this type of catalyst exhibits high activity for reducing CO 2 to CO. [10] However, such ac atalyst is generally obtained through pyrolysis of Ni, or Co-based metal-organic frameworks (MOFs) or coordination polymers. [10,11] In contrast, no Cu-based catalysts with single active sites have been developed for the pho...

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confidence: 97%

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Zhang

Hong

et al. 2019

Angewandte Chemie

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“…As illustrated in Scheme , being irradiated by visible light, the Ru(bpy) 3 2+ complex will be motivated to the excited state of Ru(bpy) 3 2+* . The Ru(bpy) 3 2+* species would then experience a reductive quenching by the electron donor TEOA to generate the reduced state [Ru(bpy) 3 ] + . Afterward, the excited electrons of the reduced ruthenium complex will delocalize and migrate to the NiCo 2 S 4 catalyst to reduce the CO 2 molecules adsorbed on the surface, leading to the CO evolution; while the photosensitizer recover to the initial state.…”

Section: Resultsmentioning

confidence: 99%

“…[57] The Ru(bpy) 3 2 + * species would then experience a reductive quenching by the electron donor TEOA to generate the reduced state [Ru(bpy) 3 ] + . [58][59][60][61][62][63] Afterward, the excited electrons of the reduced ruthenium complex will delocalize and migrate to the NiCo 2 S 4 catalyst to reduce the CO 2 molecules adsorbed on the surface, leading to the CO evolution; while the photosensitizer recover to the initial state. Alternatively, the electrons can also react with the protons existed in the catalytic system to give the formation of H 2 gas.…”

Section: Resultsmentioning

confidence: 99%

Spinel‐Type Mixed Metal Sulfide NiCo₂S₄ for Efficient Photocatalytic Reduction of CO₂ with Visible Light

et al. 2019

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Mixed metal oxides with a spinel structure have exhibited great opportunities for photocatalytic CO2 reduction; however, the abilities of their sulfide counterparts in this promising area are much less reported. Herein, we demonstrate the synthesis of a ternary metal sulfide, namely NiCo2S4, and its first application to catalyze the CO2 photoreduction reaction under visible light irradiation. The NiCo2S4 material is prepared through a coupled solvothermal‐ion exchange strategy, and is fully checked by diverse characterizations, including X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), energy‐dispersive X‐ray spectroscopy (EDX) and N2 sorption measurements. Under visible light irradiation in a classic tandem photochemical system, this non‐noble‐metal NiCo2S4 catalyst affords a considerable activity and high stability for CO2 deoxygenative reduction, delivering a high CO‐liberating rate of 43.5 μmol mg−1 h−1. The in‐situ PL and transient photocurrent measurements reveal that the spinel catalyst can hamper recombination and accelerate transfer of light‐excited charge carriers, and thus boosting the CO2 reduction reaction. At last, a possible mechanism of the NiCo2S4‐catalyzed CO2 photoreduction reaction is proposed.

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“…(1)], [125][126][127][128] DRM [Eq. (3)], [132][133][134][135][136][137][138][139][140] were reported. (3)], [132][133][134][135][136][137][138][139][140] were reported.…”

Section: Gas-solid-phase Reactionmentioning

confidence: 99%

“…Many photocatalytic materials, such as traditional TiO 2based materials, [132,133] new non-metallicg raphite-like carbon nitride materials, [134,135] metal-organic framework (MOF)c ompounds, [136,137] and even covalento rganic framework (COF) compounds, [138][139][140] have been used for this reaction. The main products are H 2 ,C O, CH 4 , and other hydrocarbons, and the most advantageous characteristics of this reaction are the use of solar heat andl ight energy.I np reviousy ears, research into the photocatalytic CDC reactiona sar educing process has received extensive attention.…”

Section: Gas-solid-phase Reactionmentioning

confidence: 99%

Bismuth‐Based Photocatalysts for Solar Photocatalytic Carbon Dioxide Conversion

et al. 2019

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Reviews Figure 5. Characterization of bulk layered Bi 12 O 17 Cl 2 nanosheets. a) SEM image, b) top-view HRTEM image,c)SAED pattern, d) side-viewH RTEM image, e) crystal orientations, f) schematicillustration, g) side-view atomic-resolution high-angle annular dark-field scanningt ransmission electron microscopy (HAADF-STEM)i mage, and h-j) corresponding electron energy-loss spectroscopy( EELS) elemental maps.T he inset in d) showst he crystals tructure of bulk layered

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Metal–organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO₂: the role of the morphology effect

Abstract: The two-dimensional ZIF-67 with a leaf-like morphology exhibited the best photocatalytic activity and stability due to the highest CO2 adsorption capability and efficient electron transfer from the excited [Ru(bpy)3]2+ to ZIF-67.

Cited by 270 publications

References 33 publications

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Spinel‐Type Mixed Metal Sulfide NiCo₂S₄ for Efficient Photocatalytic Reduction of CO₂ with Visible Light

Bismuth‐Based Photocatalysts for Solar Photocatalytic Carbon Dioxide Conversion

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Metal–organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO2: the role of the morphology effect

Abstract: The two-dimensional ZIF-67 with a leaf-like morphology exhibited the best photocatalytic activity and stability due to the highest CO2 adsorption capability and efficient electron transfer from the excited [Ru(bpy)3]2+ to ZIF-67.

Cited by 270 publications

References 33 publications

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO

Spinel‐Type Mixed Metal Sulfide NiCo2S4 for Efficient Photocatalytic Reduction of CO2 with Visible Light

Bismuth‐Based Photocatalysts for Solar Photocatalytic Carbon Dioxide Conversion

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Metal–organic frameworks (ZIF-67) as efficient cocatalysts for photocatalytic reduction of CO₂: the role of the morphology effect

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO₂ to CO

Spinel‐Type Mixed Metal Sulfide NiCo₂S₄ for Efficient Photocatalytic Reduction of CO₂ with Visible Light