Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction.
Asa W. Nichols,Charles W. Machan +1 more
Reads0
Chats0
TLDR
The development of secondary-sphere strategies to facilitate rapid and selective CO2 reduction is reviewed with an in-depth examination of the classic [Fe(tetraphenylporphyrin)]+, [Ni(cyclam)]2+, Mn(bpy)(CO)3X, and Re(b py)(CO).3X systems, including relevant highlights from other recently developed ligand platforms.Abstract:
The generation of fuels and value-added chemicals from carbon dioxide (CO2) using electrocatalysis is a promising approach to the eventual large-scale utilization of intermittent renewable energy sources. To mediate kinetically and thermodynamically challenging transformations of CO2, early reports of molecular catalysts focused primarily on precious metal centers. However, through careful ligand design, earth-abundant first-row transition metals have also demonstrated activity and selectivity for electrocatalytic CO2 reduction. A particularly effective and promising approach for enhancement of reaction rates and efficiencies of molecular electrocatalysts for CO2 reduction is the modulation of the secondary coordination sphere of the active site. In practice, this has been achieved through the mimicry of enzyme structures: incorporating pendent Bronsted acid/base sites, charged residues, sterically hindered environments, and bimetallic active sites have all proved to be valid strategies for iterative optimization. Herein, the development of secondary-sphere strategies to facilitate rapid and selective CO2 reduction is reviewed with an in-depth examination of the classic [Fe(tetraphenylporphyrin)]+, [Ni(cyclam)]2+, Mn(bpy)(CO)3X, and Re(bpy)(CO)3X (X = solvent or halide) systems, including relevant highlights from other recently developed ligand platforms.read more
Citations
More filters
Journal ArticleDOI
Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials
TL;DR: The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO2 reduction.
Journal ArticleDOI
Methanol Synthesis from CO2: A Review of the Latest Developments in Heterogeneous Catalysis.
TL;DR: The main efforts focused on the improvement of conventional Cu/ZnO based catalysts and the development of new catalytic systems targeting the specific needs for CO2 to methanol reactions (unfavourable thermodynamics, production of high amount of water and high meethanol selectivity under high or full CO2 conversion).
Journal ArticleDOI
A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
Rahman Daiyan,Wibawa Hendra Saputera,Wibawa Hendra Saputera,Hassan Masood,Josh Leverett,Xunyu Lu,Rose Amal +6 more
Journal ArticleDOI
Recent advances in metalloporphyrin-based catalyst design towards carbon dioxide reduction: from bio-inspired second coordination sphere modifications to hierarchical architectures
TL;DR: This review collects the recent advances centred around the chemistry of metalloporphyrins for the reduction of CO2.
Journal ArticleDOI
Selectivity in Electrochemical CO2 Reduction.
TL;DR: The spectroscopic data obtained from different intermediates have been identified in different CO2RR catalysts to develop an electronic structure selectivity relationship that is deemed to be important for deciding the selectivity of 2e-/2H+ CO2 RR.
References
More filters
Journal ArticleDOI
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
TL;DR: In this paper, the authors report new insights into the electrochemical reduction of CO2 on a metallic copper surface, enabled by the development of an experimental methodology with unprecedented sensitivity for the identification and quantification of CO 2 electroreduction products.
Journal ArticleDOI
Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels
TL;DR: This tutorial review will present much of the significant work that has been done in the field of electrocatalytic and homogeneous reduction of carbon dioxide over the past three decades and extend the discussion to the important conclusions from previous work and recommendations for future directions to develop a catalytic system that will convert carbon dioxide to liquid fuels with high efficiencies.
Journal ArticleDOI
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation
Aaron M. Appel,John E. Bercaw,Andrew Bruce Bocarsly,Holger Dobbek,Daniel L. DuBois,Michel Dupuis,James G. Ferry,Etsuko Fujita,Russ Hille,Paul J. A. Kenis,Cheryl A. Kerfeld,Cheryl A. Kerfeld,Robert H. Morris,Charles H. F. Peden,Archie R. Portis,Stephen W. Ragsdale,Thomas B. Rauchfuss,Joost N. H. Reek,Lance C. Seefeldt,Rudolf K. Thauer,Grover L. Waldrop +20 more
TL;DR: Providing a future energy supply that is secure and CO_2-neutral will require switching to nonfossil energy sources such as wind, solar, nuclear, and geothermal energy and developing methods for transforming the energy produced by these new sources into forms that can be stored, transported, and used upon demand.
Journal ArticleDOI
Opportunities and prospects in the chemical recycling of carbon dioxide to fuels
TL;DR: In this paper, the opportunities and prospects in the chemical recycling of carbon dioxide to fuels, as a complementary technology to carbon sequestration and storage (CSS), are analyzed, and it is remarked that the requisites for this objective are (i) minimize as much as possible the consumption of hydrogen (or hydrogen sources), (ii) produce fuels that can be easily stored and transported, and (iii) use renewable energy sources.
Related Papers (5)
A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst.
Homogeneously Catalyzed Electroreduction of Carbon Dioxide-Methods, Mechanisms, and Catalysts
Carbon dioxide activation at the Ni,Fe-cluster of anaerobic carbon monoxide dehydrogenase.
Jae-Hun Jeoung,Holger Dobbek +1 more
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation
Aaron M. Appel,John E. Bercaw,Andrew Bruce Bocarsly,Holger Dobbek,Daniel L. DuBois,Michel Dupuis,James G. Ferry,Etsuko Fujita,Russ Hille,Paul J. A. Kenis,Cheryl A. Kerfeld,Cheryl A. Kerfeld,Robert H. Morris,Charles H. F. Peden,Archie R. Portis,Stephen W. Ragsdale,Thomas B. Rauchfuss,Joost N. H. Reek,Lance C. Seefeldt,Rudolf K. Thauer,Grover L. Waldrop +20 more