This paper reviews recent progress made in identifying electrocatalysts for carbon dioxide (CO2) reduction to produce low-carbon fuels, including CO, HCOOH/HCOO−, CH2O, CH4, H2C2O4/HC2O4−, C2H4, CH3OH, CH3CH2OH and others. The electrocatalysts are classified into several categories, including metals, metal alloys, metal oxides, metal complexes, polymers/clusters, enzymes and organic molecules. The catalyts' activity, product selectivity, Faradaic efficiency, catalytic stability and reduction mechanisms during CO2 electroreduction have received detailed treatment. In particular, we review the effects of electrode potential, solution–electrolyte type and composition, temperature, pressure, and other conditions on these catalyst properties. The challenges in achieving highly active and stable CO2 reduction electrocatalysts are analyzed, and several research directions for practical applications are proposed, with the aim of mitigating performance degradation, overcoming additional challenges, and facilitating research and development in this area.

A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels

4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20133-173.pdf

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

Two major energy-related problems confront the world in the
next 50 years. First, increased worldwide competition for
gradually depleting fossil fuel reserves (derived from past
photosynthesis) will lead to higher costs, both monetarily and politically. Second, atmospheric CO_2 levels are at their highest recorded level since records began. Further increases are predicted to produce large and uncontrollable impacts on the world climate. These projected impacts extend beyond climate to ocean acidification, because the ocean is a major sink for atmospheric CO2.1 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.

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation

/pdf/advances-in-transition-metal-pd-ni-fe-catalyzed-cross-46kfk7jmlm.pdf

Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners.

Helicates as Versatile Supramolecular Complexes.

4'-Vinyl-2,2':6',2''-terpyridinyl was conveniently prepared from 2-acetylpyridine via -oxoketene dithioacetal methodology, the intermediate 4'-(methylthio)-2,2':6',2''-terpyridinyl being converted into the corresponding 4'-methyl derivative with methylmagnesium bromide and bis(triphenylphosphino)nickel(II) dichloride followed by generation of the methyl anion with lithium tetramethylpiperidide, reaction of the anion with chloromethyl methyl ether, and introduction of the vinyl group by treatment of the ether with potassium tert-butoxide/THF. Analogous reactions led to the 4-vinyl- and 6-vinyl isomers by using the appropriate methyl-substituted 2-acetylpyridine except that in these instances desulfurization of the 4'-methylthio group with nickel boride was an addition step. These vinyl-substituted ligands formed a variety of readily electropolymerizable simple and mixed-ligand complex monomers with cobalt, ruthenium, and iron with polymerization rates whose magnitude varied with position and number of vinyl substituents.

4-Vinyl-, 6-vinyl-, and 4'-vinyl-2,2':6',2"-terpyridinyl ligands: their synthesis and the electrochemistry of their transition-metal coordination complexes

Electrocatalysis of CO2 Reduction in Aqueous Media at Electrodes Modified with Electropolymerized Films of Vinylterpyridine Complexes of Transition Metals

There has been, in the recent past, much interest in the design of electrocatalysts for the reduction carbon dioxide to useful fuel products. These reactions are particularly difficult to catalyze since they not only involve multiple electron transfers but also are often coupled with chemical steps such as protonation. Furthermore, there can be multiple and competing reaction pathways giving rise to a variety and distribution of reaction products. The authors have prepared a wide variety of first-row transition-metal complexes that incorporate bis(terdentate) coordination around the metal center. The authors find that all of these materials exhibit some degree of electrocatalytic activity in the reduction of CO{sub 2}. The author describes preliminary observations and point to some future directions.

Electrocatalytic reduction of carbon dioxide with iron, cobalt, and nickel complexes of terdentate ligands

Spontaneous self-assembly of functionalized quaterpyridines and quinquepyridines at ambient temperature in the presence of an appropriate copper ion resulted in a versatile group of multimetallic, double-stranded helical complexes. Methylthio-substituted quaterpyridine and copper ion gave a bimetallic complex with Cu(I) and a monometallic complex with Cu(II). Redox state-induced transformations between these complexes were demonstrated chemically and verified spectroelectrochemically. The [LCu I ] 2 °PF 6 ] 2 complex crystallized in the monoclinic space group 12/a

Metal ion-induced self-assembly of functionalized 2,6-oligopyridines. 2. Copper-containing double-stranded helicates derived from functionalized quaterpyridine and quinquepyridine: redox state-induced transformations and electron communication in mixed-valence systems

By applying a combination of triflate, vinyltin, and Pd° chemistry, we have resolved this problem in the terpyridine series, and a convenient synthesis of 4'-vinylterpy from ethyl 2-pyridinecarboxylate in a reasonable overall yield is described in this paper

Kevin T. Potts

Papers

4-Vinyl-, 6-vinyl-, and 4'-vinyl-2,2':6',2"-terpyridinyl ligands: their synthesis and the electrochemistry of their transition-metal coordination complexes

Electrocatalysis of CO2 Reduction in Aqueous Media at Electrodes Modified with Electropolymerized Films of Vinylterpyridine Complexes of Transition Metals

Electrocatalytic reduction of carbon dioxide with iron, cobalt, and nickel complexes of terdentate ligands

Metal ion-induced self-assembly of functionalized 2,6-oligopyridines. 2. Copper-containing double-stranded helicates derived from functionalized quaterpyridine and quinquepyridine: redox state-induced transformations and electron communication in mixed-valence systems

Synthesis of 4'-vinyl-2,2':6'2″-terpyridine