Spatial Confinement in Copper-Porphyrin Frameworks Enhances Carbon Dioxide Reduction to Hydrocarbons

Zhou, Yinzheng; Chen, Shenghua; Xi, Shibo; Wang, Zhitong; Deng, Peilin; Yang, Fan; Han, Youjia; Pang, Yuanjie; Xia, Bao Yu

doi:10.1016/j.xcrp.2020.100182

Cited by 36 publications

(23 citation statements)

References 46 publications

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“…On the basis of linkage of −COOH and the Cu ion, 2D CuTCPP NSs can be easily synthesized via the solvothermal method (see the Experimental Section for details) Figure a presents that as-prepared NSs are very smooth, and their size is up to microns.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Synthesis of 2D CuTCPP NSs. 33 In this experiment, 26.4 mg of CuTCPP (0.03 mmol) and 27.6 mg of Cu(NO 3 ) 2 •3H 2 O (0.03 mmol) were dissolved in the mixing solution of 9.0 mL of dimethylformamide (DMF) and 3.0 mL of ethanol and were sonicated for 30 min. Then, the solution was heated to 120 °C for 12 h and naturally cooled to room temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

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Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Tao

et al. 2021

Crystal Growth & Design

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A variety of organic semiconductor nanostructures have been already reported for photoelectric applications; however, there are a few systematic studies on the dependence of their photocurrent on nanostructures. Here, 0D, 1D, 2D, and 3D nanostructures of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin copper (CuTCPP) are successfully constructed via liquid-phase chemical methods. Structural characterization shows that 0D and 1D nanostructures should result from the π−π stacking of CuTCPP molecules, while 2D and 3D ones are mainly from the in-plane aggregation via the linkage of −COOH with the Cu ion. The photoelectric properties of CuTCPP-based nanostructures are investigated to evaluate the effect of shape, size, and structure. A huge difference in photocurrent response is found, as compared to the raw material (0.09 μA/cm 2 ) and 0D (0.17 μA/cm 2 ), 1D (2.24 μA/cm 2 ), 2D (0.4 μA/cm 2 ), and 3D (0.93 μA/cm 2 ) nanostructures. Further study reveals that the 1D nanostructure exhibits the lowest impedance and the longest exciton lifetime, strongly indicating that the photocurrent of the metal porphyrin nanostructure should be mainly limited in an in-plane exciton with a shorter lifetime than in an intermolecular one. This work provides a clear strategy to design molecule-based photoelectric nanomaterials.

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Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Tao

et al. 2021

Crystal Growth & Design

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“…For example, a MOF-templated copper porphyrin catalyzed the CO 2 reduction to methane and ethylene. The spatial arrangement of copper sites was claimed to be crucial for hydrocarbon production . This claim might be supported by the study of Jeong et al where the C 2 products of CO 2 reductions were favored by tuning the atomic-scale spacing between deposited copper atoms.…”

Section: Open Questions Challenges and Perspectivesmentioning

confidence: 91%

“…The spatial arrangement of copper sites was claimed to be crucial for hydrocarbon production. 112 This claim might be supported by the study of Jeong et al 113 where the C 2 products of CO 2 reductions were favored by tuning the atomic-scale spacing between deposited copper atoms. Cu-MOF-derived catalysts obtained by the carbonization of a Cu-based MOF, (Cu(II) benzene-1,3,5-tricarboxylate (BTC), HKUST-1) yielded highly selective liquid products (methanol and ethanol) 114 and ethylene.…”

Section: The Effect Of Ligand Structure Of Cu Complexes On Co 2 Reduc...mentioning

confidence: 93%

Electrochemical CO₂ Reduction Catalyzed by Copper Molecular Complexes: The Influence of Ligand Structure

Kim

Wagner

et al. 2022

Energy Fuels

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Inexpensive and earth abundant copper complexes are popular choices to catalyze the electrochemical conversion of carbon dioxide (CO 2 ) into value-added products. Cu complexes have been applied in homogeneous catalysis dissolved in solutions or in heterogeneous catalysis immobilized on electrode surfaces. The aim of this review is to examine correlations between the ligand structures of the Cu complexes on the CO 2 reduction product selectivity in both homogeneous and heterogeneous applications. This review covers nine main categories of Cu complexes grouped by their ligand structures, enabling the comparisons among small and large complexes, mononuclear or dinuclear complexes, and complexes with different geometry/ number of ligand binding sites. In homogeneous catalytic systems, small mononuclear Cu complexes tend to favor carbon monoxide or formate production, whereas dinuclear complexes based on a disulfanediyl ligand produced oxalate through carbon−carbon coupling. In heterogeneous catalysis, macrocyclic ligand-containing Cu complexes and dinuclear complexes were able to produce higher carbon products of ethanol and ethylene. However, establishing robust correlations between molecular geometry, coordination numbers or the denticity of the ligands and the CO 2 reduction pathways are difficult, because tetrahedral complexes were mostly applied in homogeneous systems while square planar complexes in heterogeneous systems. A third of the examined Cu complexes formed Cu complex-derived catalysts on the electrode surface, which may affect product selectivity. Despite the complex behavior of CO 2 reduction systems based on Cu complex catalysts, molecular structure−property correlations uncovered in this comprehensive review are expected to help researchers design new complexes tailored for CO 2 reduction realizing high selectivity in both homogeneous and heterogeneous systems. The design of new complexes should be guided by combinatorial studies to discover robust correlations in the multidimensional space of molecular structure−electrochemical CO 2 reduction conditions−product selectivity and efficiency of electrochemical CO 2 reduction.

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“…Simultaneously, the periodically nanoporous structures can provide i) uniform reaction microenvironment to favor high product selectivity and ii) nano-confinement of substrates and intermediates to facilitate their deep reduction. [104] Reticular materials allow for high-density integration of molecular catalysts. Of note, 2D reticular material are typically stacked in AA mode, which may hinder sterical accessibility of active sites.…”

Section: Reticular Chemistrymentioning

confidence: 99%

Electrocatalytic CO₂Reduction: from Discrete Molecular Catalysts to Their Integrated Catalytic Materials

Lei

Xia

2022

Chemistry A European J

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Molecular catalysts (metal complexes), with molecularly defined uniform active sites and atomically precise structural tailorability allowing for regulating catalytic performance through metal‐ and ligand‐centered engineering and elucidating reaction mechanisms via routine photoelectrochemical characterizations, have been increasingly explored for electrocatalytic CO2 reduction (ECR). However, their poor stability and low catalytic current density are undesirable for practical applications. Heterogenizing discrete molecular catalysts can potentially surmount these issues, and the resulting integrated catalysts largely share catalytical properties with their discrete molecular counterparts, which bridge the gap between heterogeneous and homogeneous catalysis and combine their advantages. This minireview surveys advances in design and regulation of molecular catalysts such as porphyrin, phthalocyanine, and bipyridine‐based metal complexes and their integrated catalytic materials for selective ECR.

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Spatial Confinement in Copper-Porphyrin Frameworks Enhances Carbon Dioxide Reduction to Hydrocarbons

Cited by 36 publications

References 46 publications

Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Electrochemical CO₂ Reduction Catalyzed by Copper Molecular Complexes: The Influence of Ligand Structure

Electrocatalytic CO₂Reduction: from Discrete Molecular Catalysts to Their Integrated Catalytic Materials

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Spatial Confinement in Copper-Porphyrin Frameworks Enhances Carbon Dioxide Reduction to Hydrocarbons

Cited by 36 publications

References 46 publications

Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Controllable Synthesis and Effects of Porphyrin Copper Nanostructures on Photoelectric Properties

Electrochemical CO2 Reduction Catalyzed by Copper Molecular Complexes: The Influence of Ligand Structure

Electrocatalytic CO2Reduction: from Discrete Molecular Catalysts to Their Integrated Catalytic Materials

Contact Info

Product

Resources

About

Electrochemical CO₂ Reduction Catalyzed by Copper Molecular Complexes: The Influence of Ligand Structure

Electrocatalytic CO₂Reduction: from Discrete Molecular Catalysts to Their Integrated Catalytic Materials