Selectivity in Electrochemical CO₂ Reduction

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(2), P. 134 - 144

Published: Jan. 6, 2022

The electrocatalytic CO2 reduction reaction (CO2RR) to generate fixed forms of carbons that have commercial value is a lucrative avenue ameliorate the growing concerns about detrimental effect emissions as well carbon-based feed chemicals, which are generally obtained from petrochemical industry. area electrochemical CO2RR has seen substantial activity in past decade, and several good catalysts been reported. While focus was initially on rate overpotential electrocatalysis, it gradually shifting toward more chemically challenging issue selectivity. can be partially reduced produce C1 products like CO, HCOOH, CH3OH, etc. before its complete 8e-/8H+ CH4. In addition that, low-valent electron-rich metal centers deployed activate CO2, Lewis acid, prone reduce protons, substrate for CO2RR, leading competing hydrogen evolution (HER). Similarly, oxidation by atmospheric O2 (i.e., catalyze oxygen reaction, ORR), necessitating strictly anaerobic conditions CO2RR. Not only requirement O2-free impractical, but also leads release species such O2-, H2O2, etc., reactive result oxidative degradation catalyst.In this Account, mechanistic investigations detecting and, often, trapping characterizing intermediates used understand factors determine selectivity spectroscopic data different identified develop an electronic structure relationship deemed important deciding 2e-/2H+ roles played spin state, bonding, heterogenization determining (producing or CH4) discussed using examples both iron porphyrin non-heme bioinspired artificial mimics. addition, strategies demonstrated where competition between HER ORR could skewed overwhelmingly favor cases.

Language: Английский

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Transition Metal Complexes as Catalysts for the Electroconversion of CO₂: An Organometallic Perspective

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(21), P. 11628 - 11686

Published: Jan. 19, 2021

The electrocatalytic transformation of carbon dioxide has been a topic interest in the field CO2 utilization for long time. Recently, area seen increasing dynamics as an alternative strategy to catalytic hydrogenation reduction. While many studies focus on direct electron transfer molecule at electrode material, molecular transition metal complexes solution offer possibility act catalysts transfer. C1 compounds such monoxide, formate, and methanol are often targeted main products, but more elaborate transformations also possible within coordination sphere center. This perspective article will cover selected examples illustrate categorize currently favored mechanisms electrochemically induced promoted by homogeneous complexes. insights be corroborated with concepts elementary steps organometallic catalysis derive potential strategies broaden diversity products.

Language: Английский

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Highly Efficient Electrocatalytic CO₂ Reduction to C₂₊ Products on a Poly(ionic liquid)‐Based Cu⁰–Cu^I Tandem Catalyst

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(9)

Published: Dec. 1, 2021

Electroreduction of CO2 on a polymer-modified Cu-based catalyst has shown high multi-electron reduction (>2 e- ) selectivity, however, most the corresponding current densities are still too small to support industrial applications. In this work, we designed poly(ionic liquid) (PIL)-based Cu0 -CuI tandem for production C2+ products with both reaction rate and selectivity. Remarkably, faradaic efficiency (FE 76.1 % partial density 304.2 mA cm-2 is obtained. Mechanistic studies reveal numbers highly dispersed -PIL-CuI interfaces vital such reactivity. Specifically, Cu nanoparticles derived -PIL account moderate whereas CuI species PIL-CuI exhibit activity C-C coupling local enriched *CO intermediate. Furthermore, presence PIL layer promotes selectivity by lowering barrier coupling.

Language: Английский

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Recent Advances of Magnetite (Fe3O4)-Based Magnetic Materials in Catalytic Applications

Magnetochemistry, Journal Year: 2023, Volume and Issue: 9(4), P. 110 - 110

Published: April 20, 2023

Catalysts play a critical role in producing most industrial chemicals and are essential to environmental remediation. Under the demands of sustainable development, environment protection, cost-related factors, it has been suggested that catalysts sufficiently separable conveniently recyclable catalysis process. Magnetite (Fe3O4) nanomaterials provide possible way achieve this goal, due their magnetism, chemical stability, low toxicity, economic viability, etc. Therefore, Fe3O4-based materials emerging as an important solid support load heterogeneous immobilize homogeneous catalysts. Moreover, addition magnetic character will not only make recovery much easier but also possibly endow with desirable properties, such magnetothermal conversion, Lewis acid, mimetic enzyme activity, Fenton activity. The following review comprises short survey recent reports catalytic applications materials. It contains seven sections, introduction into theme, remediation, electrocatalysis, organic synthesis, synthesis biodiesel, cancer treatment, conclusions about reported research perspectives for future developments. Elucidation functions mechanisms Fe3O4 nanoparticles (NPs) these may benefit acquisition robust affordable protocols, leading good activity enhanced recoverability.

Language: Английский

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Utilization of Low-Concentration CO₂ with Molecular Catalysts Assisted by CO₂-Capturing Ability of Catalysts, Additives, or Reaction Media

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(15), P. 6640 - 6660

Published: April 11, 2022

Increasing concentration of atmospheric CO2 is a worldwide concern and continues to trigger various environmental problems. Photo- or electrocatalytic reduction (CO2-Red) using solar energy, i.e., artificial photosynthesis, prospective technique owing its sustainability the usefulness reaction products. Concentrations in exhaust gases from industries are several % 20%, that atmosphere about 400 ppm. Although condensation processes require high energy consumption cost, pure has been used most reported studies for photo- CO2-Red because between catalyst could be one rate-limiting steps. To address these issues provide repository potential techniques other researchers, this perspective summarizes catalytic systems low-concentration CO2, which utilize combination CO2-capturing reactions (or adsorption). First, we describe insertions into M–X bonds catalysts, increase rate constants and/or equilibrium binding on modifications second coordination sphere stabilize CO2-bound catalysts. Furthermore, discuss media have unique effect increasing concentrations around These include typical additives, ionic liquids, metal–organic frameworks.

Language: Английский

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Challenges and recent advancements in the transformation of CO₂into carboxylic acids: straightforward assembly with homogeneous 3d metals

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(22), P. 9371 - 9423

Published: Jan. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Language: Английский

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Electrocarboxylation of Aryl Epoxides with CO₂for the Facile and Selective Synthesis of β‐Hydroxy Acids

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: July 30, 2022

Abstract Herein, an efficient and facile approach to valuable β‐hydroxy acid derivatives from readily available aryl epoxides CO 2 with high chemo‐ regioselectivity under mild sustainable electrochemical conditions is described. This showed broad substrate scope good functional‐group compatibility. In addition epoxides, four‐ six‐membered cyclic ethers could all be tolerated in the reaction provide synthetically useful hydroxy acids efficiency. Further late‐stage carboxylation of complex molecules drug demonstrated its potential application pharmaceutical industry. Mechanistic studies disclosed possible pathways.

Language: Английский

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Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO₂ Reduction Catalyzed by Iron Porphyrins

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(26), P. 11656 - 11663

Published: June 24, 2022

Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO2 reduction, particularly heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate organic and its roles homogeneous electrocatalysis remain underexplored. Here, we investigate influence on iron porphyrin-catalyzed reduction. We show that is a viable proton donor electrolyte (pKa = 20.8 dimethyl sulfoxide) urea pendants second coordination sphere can be used template vicinity molecular porphyrin catalyst. The templated binding increases acidity, resulting 1500-fold enhancement rates unmodified parent porphyrin. This work emphasizes importance speciation wet establishes second-sphere templating as design strategy harness this adventitious acid enhance reduction catalysis.

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2728 - 2745

Published: Sept. 3, 2024

ConspectusCarbon dioxide (CO

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