scholarly journals A review on the state-of-the-art advances for CO2 electro-chemical reduction using metal complex molecular catalysts

2019 ◽  
Vol 44 (1) ◽  
pp. 11
Author(s):  
Hitler Louis ◽  
Ozioma Udochukwu Akakuru ◽  
Philip Monday ◽  
Oyebanji Oluwatomisin Funmilayo
Keyword(s):  
Metal Complex ◽  
Theoretical Calculations ◽  
Chemical Reduction ◽  
Co2 Reduction ◽  
Molecular Catalyst ◽  
Global Problems ◽  
Carbon Dioxide Co2 ◽  
Molecular Catalysts ◽  
Reduction Catalysts

Significantly, global warming which is caused by CO2 emission and energy shortage are global problems resulting from artificial photosynthesis because it required many functions (light harvesting, Z water, and oxidation scheme). Therefore, photocatalytic systems development for CO2 reduction is germane in this field. Metal complexes molecular catalyst have become prevalent homogeneous catalysts for carbon dioxide (CO2) photocatalytic reduction since it was initially known as CO2 reduction catalysts in the 70s and the 80s, while utmost part involved macrocyclic cobalt(II) and nickel(II) complexes. This review article presents a broad understanding on some active catalysts recently reported as a metal complex molecular catalytic schemes for CO2 reduction, alongside catalytic activity, stability, selectivity under electro-reduction, and photoreduction circumstances. The progress of in situ spectroelectrochemical methods, typically supported via theoretical calculations, helped to access this know-how by providing information which enabled researchers to acquire more in-depth perception into unveiling the catalytic reaction and mechanisms intermediates.

Bio-proton coupled semiconductor/metal-complex hybrid photoelectrocatalytic interface for efficient CO2 reduction

2019 ◽  
Vol 21 (2) ◽  
pp. 339-348 ◽  
Author(s):  
Jibo Liu ◽  
Chenyan Guo ◽  
Xiaojun Hu ◽  
Guohua Zhao
Keyword(s):  
Proton Transfer ◽  
Metal Complex ◽  
High Efficiency ◽  
Co2 Reduction ◽  
Semiconductor Substrate ◽  
Molecular Catalyst ◽  
Proton Coupling ◽  
Complex Hybrid ◽  
Complex Semiconductor

Aimed at high-efficiency biomimetic CO2 photoelectrochemical conversion, a bio-proton coupling metal-complex/semiconductor hybrid photoelectrocatalytic interface (Ru-BNAH/TiO2/Cu2O) was constructed by covalently modifying an in situ proton-transfer functionized molecular catalyst (Ru-BNAH) on the surface of a TiO2/Cu2O composite semiconductor substrate electrode.

Molecular electrocatalysts can mediate fast, selective CO2 reduction in a flow cell

Science ◽  
2019 ◽  
Vol 365 (6451) ◽  
pp. 367-369 ◽  
Author(s):  
Shaoxuan Ren ◽  
Dorian Joulié ◽  
Danielle Salvatore ◽  
Kristian Torbensen ◽  
Min Wang ◽  
...  
Keyword(s):  
Flow Reactor ◽  
Co2 Reduction ◽  
Reduction Reaction ◽  
Operating Conditions ◽  
High Current ◽  
Membrane Flow ◽  
Molecular Catalyst ◽  
Current Densities ◽  
Molecular Catalysts ◽  
Distinct Approach

Practical electrochemical carbon dioxide (CO2) conversion requires a catalyst capable of mediating the efficient formation of a single product with high selectivity at high current densities. Solid-state electrocatalysts achieve the CO2 reduction reaction (CO2RR) at current densities ≥ 150 milliamperes per square centimeter (mA/cm2), but maintaining high selectivities at high current densities and efficiencies remains a challenge. Molecular CO2RR catalysts can be designed to achieve high selectivities and low overpotentials but only at current densities irrelevant to commercial operation. We show here that cobalt phthalocyanine, a widely available molecular catalyst, can mediate CO2 to CO formation in a zero-gap membrane flow reactor with selectivities > 95% at 150 mA/cm2. The revelation that molecular catalysts can work efficiently under these operating conditions illuminates a distinct approach for optimizing CO2RR catalysts and electrolyzers.

scholarly journals Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

2020 ◽  
Author(s):  
Josh D. B. Koenig ◽  
Zachary Dubrawski ◽  
Keerthan Rao ◽  
Janina Willkomm ◽  
Benjamin S. Gelfand ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Density Functional ◽  
Chemical Reduction ◽  
Critical Role ◽  
Co2 Reduction ◽  
Perylene Diimide ◽  
Co2 Conversion ◽  
Faradaic Efficiency ◽  
Molecular Catalyst ◽  
Controlled Potential

Here we report on a molecular catalyst with a built-in electron-reservoir for enhanced CO2 conversion. The synthesis and characterization of this N-annulated perylene diimide (PDI) photosensitized Re(bpy) supramolecular dyad [Re(bpy-TAz-PDI)], as well as successful electro- and photocatalytic CO2-to-CO conversion, are detailed herein. Upon electrochemical reduction in the presence of CO2 and a proton source, Re(bpy-TAz-PDI) exhibited significant current enhancement, where the onset of electrocatalytic CO2 reduction for Re(bpy-TAz-PDI) occurred at a much less negative potential than standard Re(bpy) complexes. At an applied potential of -1.8 V vs. Fc+/0, 400 mV lower than the benchmark Re(dmbpy) catalyst, Re(bpy-TAz-PDI) was able to achieve the same catalytic activity (TONco = 24) and Faradaic efficiency (FE = 92 %) during controlled potential electrolysis (CPE) experiments. Through a combination of UV-visible-nearIR spectroelectrochemistry (SEC), FTIR SEC, and chemical reduction experiments, it was shown that the PDI-moiety served as an electron-reservoir for Re(bpy), thereby allowing catalytic activity at lower overpotentials. Density functional theory (DFT) studies probing the optimized geometries, frontier molecular orbitals, and spin-densities of various catalytic intermediates revealed that the geometric configuration of PDI, relative to the Re(bpy)-moiety, plays a critical role in accessing electrons from the electron-reservoir. The near identical performance of Re(bpy-TAz-PDI) at lower overpotentials relative to the benchmark Re(dmbpy) catalyst highlights the utility of organic chromophore electron-reservoirs as a method for lowering the required overpotential for CO2 conversion. <br>

scholarly journals Bioinspired cobalt cubanes with tunable redox potentials for photocatalytic water oxidation and CO2 reduction

2018 ◽  
Vol 14 ◽  
pp. 2331-2339
Author(s):  
Zhishan Luo ◽  
Yidong Hou ◽  
Jinshui Zhang ◽  
Sibo Wang ◽  
Xinchen Wang
Keyword(s):  
Water Oxidation ◽  
Function Analysis ◽  
Co2 Reduction ◽  
Energy Utilization ◽  
Modulation Method ◽  
Redox Potentials ◽  
Molecular Catalyst ◽  
Selective Ligand ◽  
Earth Abundant ◽  
Molecular Catalysts

The development of efficient, robust and earth-abundant catalysts for photocatalytic conversions has been the Achilles’ heel of solar energy utilization. Here, we report on a chemical approach based on ligand designed architectures to fabricate unique structural molecular catalysts coupled with appropriate light harvesters (e.g., carbon nitride and Ru(bpy)3 2+) for photoredox reactions. The “Co4O4” cubane complex Co4O4(CO2Me)4(RNC5H4)4 (R = CN, Br, H, Me, OMe), serves as a molecular catalyst for the efficient and stable photocatalytic water oxidation and CO2 reduction. A comprehensive structure–function analysis emerged herein, highlights the regulation of electronic characteristics for a molecular catalyst by selective ligand modification. This work demonstrates a modulation method for fabricating effective, stable and earth-abundant molecular catalysts, which might facilitate further innovation in the function-led design and synthesis of cubane clusters for photoredox reactions.

scholarly journals Stabilization Effects in Binary Colloidal Cu and Ag Nanoparticle Electrodes under Electrochemical CO2 Reduction Conditions

Nanoscale ◽  
2021 ◽  
Author(s):  
Longfei Wu ◽  
Kees Kolmeijer ◽  
Yue Zhang ◽  
Hongyu An ◽  
Sven Arnouts ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Electrochemical Reaction ◽  
Co2 Reduction ◽  
Modified Electrodes ◽  
Ag Nanoparticle ◽  
Reaction Conditions ◽  
Electrochemical Co2 Reduction ◽  
Carbon Dioxide Co2 ◽  
Reduction Catalysts ◽  
Sintering Processes

Nanoparticle modified electrodes constitute an attractive way to tailor-make efficient carbon dioxide (CO2) reduction catalysts. However, the restructuring and sintering processes of nanoparticles under electrochemical reaction conditions not only impedes...

scholarly journals Electrochemical C2 Production from CO2 via Self-Assembled Nanoparticles of Cuprous Coordination Polymer

2020 ◽  
Author(s):  
Naonari Sakamoto ◽  
Yusaku F. Nishimura ◽  
Takamasa Nonaka ◽  
Masataka Ohashi ◽  
Nobuhiro Ishida ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Complex Structure ◽  
Co2 Reduction ◽  
Reduction Reaction ◽  
Active Species ◽  
Metal Catalyst ◽  
Faradaic Efficiency ◽  
Self Assembled ◽  
Molecular Catalysts ◽  
Reduction Catalysts

Copper (Cu) metal electrocatalysts activate the CO2 reduction reaction to produce multi electron reductants; however, the instability of the copper active species causes a change in reaction selectivity. Molecular catalysts can be designed as CO2 reduction catalysts with high selectivity, although the production of multi-electron reductants (>2e-) while maintaining the catalyst structure remains difficult. Here we present self-assembled nanoparticles of a cuprous coordination polymer (Cu-SCP) that can catalyze CO2 electrochemical reduction to C2 products, such as ethylene and ethanol, with a total faradaic efficiency of 55%. Cu-SCP maintains its metal complex structure and the Cu (I) oxidation state throughout the reaction. The Cu-SCP catalyst has advantages of being both a molecular and metal catalyst, which should open up new possibilities for CO2 reduction catalysts. <br>

scholarly journals A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5524
Author(s):  
Kirill V. Kholin ◽  
Mikhail N. Khrizanforov ◽  
Vasily M. Babaev ◽  
Guliya R. Nizameeva ◽  
Salima T. Minzanova ◽  
...  
Keyword(s):  
Co2 Reduction ◽  
Reduction Reaction ◽  
Water Soluble ◽  
Molecular Catalyst ◽  
Electrochemical Catalyst ◽  
Highly Active ◽  
Electrochemical Co2 Reduction ◽  
The Stability ◽  
Molecular Catalysts ◽  
Co2 Reduction Reaction

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO2 reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO2 to CH4 in water. Stability and selectivity of conversion of CO2 to CH4 as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO2 reduction reaction (CO2RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm2 current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO2). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.

scholarly journals Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

2020 ◽  
Author(s):  
Josh D. B. Koenig ◽  
Zachary Dubrawski ◽  
Keerthan Rao ◽  
Janina Willkomm ◽  
Benjamin S. Gelfand ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Density Functional ◽  
Chemical Reduction ◽  
Critical Role ◽  
Co2 Reduction ◽  
Perylene Diimide ◽  
Co2 Conversion ◽  
Faradaic Efficiency ◽  
Molecular Catalyst ◽  
Controlled Potential

Here we report on a molecular catalyst with a built-in electron-reservoir for enhanced CO2 conversion. The synthesis and characterization of this N-annulated perylene diimide (PDI) photosensitized Re(bpy) supramolecular dyad [Re(bpy-TAz-PDI)], as well as successful electro- and photocatalytic CO2-to-CO conversion, are detailed herein. Upon electrochemical reduction in the presence of CO2 and a proton source, Re(bpy-TAz-PDI) exhibited significant current enhancement, where the onset of electrocatalytic CO2 reduction for Re(bpy-TAz-PDI) occurred at a much less negative potential than standard Re(bpy) complexes. At an applied potential of -1.8 V vs. Fc+/0, 400 mV lower than the benchmark Re(dmbpy) catalyst, Re(bpy-TAz-PDI) was able to achieve the same catalytic activity (TONco = 24) and Faradaic efficiency (FE = 92 %) during controlled potential electrolysis (CPE) experiments. Through a combination of UV-visible-nearIR spectroelectrochemistry (SEC), FTIR SEC, and chemical reduction experiments, it was shown that the PDI-moiety served as an electron-reservoir for Re(bpy), thereby allowing catalytic activity at lower overpotentials. Density functional theory (DFT) studies probing the optimized geometries, frontier molecular orbitals, and spin-densities of various catalytic intermediates revealed that the geometric configuration of PDI, relative to the Re(bpy)-moiety, plays a critical role in accessing electrons from the electron-reservoir. The near identical performance of Re(bpy-TAz-PDI) at lower overpotentials relative to the benchmark Re(dmbpy) catalyst highlights the utility of organic chromophore electron-reservoirs as a method for lowering the required overpotential for CO2 conversion. <br>

scholarly journals Electrochemical C2 Production from CO2 via Self-Assembled Nanoparticles of Cuprous Coordination Polymer

2020 ◽  
Author(s):  
Naonari Sakamoto ◽  
Yusaku F. Nishimura ◽  
Takamasa Nonaka ◽  
Masataka Ohashi ◽  
Nobuhiro Ishida ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Complex Structure ◽  
Co2 Reduction ◽  
Reduction Reaction ◽  
Active Species ◽  
Metal Catalyst ◽  
Faradaic Efficiency ◽  
Self Assembled ◽  
Molecular Catalysts ◽  
Reduction Catalysts

Copper (Cu) metal electrocatalysts activate the CO2 reduction reaction to produce multi electron reductants; however, the instability of the copper active species causes a change in reaction selectivity. Molecular catalysts can be designed as CO2 reduction catalysts with high selectivity, although the production of multi-electron reductants (>2e-) while maintaining the catalyst structure remains difficult. Here we present self-assembled nanoparticles of a cuprous coordination polymer (Cu-SCP) that can catalyze CO2 electrochemical reduction to C2 products, such as ethylene and ethanol, with a total faradaic efficiency of 55%. Cu-SCP maintains its metal complex structure and the Cu (I) oxidation state throughout the reaction. The Cu-SCP catalyst has advantages of being both a molecular and metal catalyst, which should open up new possibilities for CO2 reduction catalysts. <br>

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