Facilitated carbon dioxide reduction using a Zn(<scp>ii</scp>) complex

Donovan, Elizabeth S.; Barry, Brian M.; Larsen, Christopher A.; Wirtz, Melissa N.; Geiger, William E.; Kemp, Richard A.

doi:10.1039/c5cc07318a

Cited by 34 publications

(34 citation statements)

References 39 publications

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“…Initially, we limited electrochemical experiments to include only complexes persistent enough to reveal crystallographic evidence of CO 2 adduct formation, but eventually extended these experiments to various Zn complexes which demonstrated more fleeting CO 2 interactions via FT-IR. One of these complexes [Zn(2-pyPPh 2 ) 2 Cl 2 (py = pyridyl)] that exhibited a short-lived CO 2 interaction proved to be an effective and robust catalyst for the conversion of CO 2 to CO, [9] which is consistent with other reports that a weak interaction between the catalyst and CO 2 is actually a desirable attribute for catalytic CO 2 transformations [10]. For example, the compound seen in Fig.…”

Section: Introductionsupporting

confidence: 77%

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Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Bruggen

Feller

Schickel

et al. 2017

MGC

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Abstract.A series of Group 13 complexes MLX 2 (M = Al or Ga, L = SC 6 H 4 -2-P t Bu 2 or OC 6 H 4 -2-P t Bu 2 , X = Me or C 6 F 5 ) have been synthesized and characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction. Reactions of Me 3 Al or Me 3 Ga with an equivalent of either 2-t Bu 2 P(C 6 H 4 )OH (1) or 2-t Bu 2 P(C 6 H 4 )SH (5) resulted in the formation of four new (2,3,6, and 7), 4-coordinate dimethyl chelate (S,P or O,P) complexes via methane elimination. The dimethyl gallium complexes (3 and 7) underwent a further reaction with excess B(C 6 F 5 ) 3 , and through ligand exchange (methyl/pentafluorophenyl), resulted in the disubstituted bis(pentafluorophenyl) analogs (4 and 8). Cyclic voltammetry (CV) experiments for all compounds in the presence of and the absence of (1-8) CO 2 were performed. For compounds showing cathodic reduction waves under CO 2 (2,3,4, and 6), bulk electrolysis experiments were performed. Electrochemical studies indicate that, for several compounds, a transient CO 2 adduct is formed which undergoes a one-electron, irreversible (or partially irreversible) reduction to form an unstable radical anion.

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Section: Introductionsupporting

confidence: 77%

“…In another example, [9] our group synthesized a Zn complex ([Ph 2 Ppy] 2 ZnCl 2 , py = 2-pyridyl) which showed no evidence of CO 2 interaction via NMR, even when experiments were performed at 100 psig CO 2 and at -48…”

Section: Co 2 Reactivity Studiesmentioning

confidence: 99%

Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Bruggen

Feller

Schickel

et al. 2017

MGC

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“… 34 Notably, a recent study highlighted an organometallic Zn complex that can activate CO 2 for electroreduction through Lewis acid–base interactions. 35 The exact role of the Zn center in our catalyst structure warrants further investigation.…”

Section: Resultsmentioning

confidence: 99%

Electroreduction of CO₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

et al. 2017

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Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at −1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.

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“…Some other organic–ligand based complexes have also been investigated as molecular electrocatalysts. Donovan et al synthesized two new Zn(II) complexes with phosphine groups and evaluated their ability to reduce CO 2 to CO . Kang et al reported an iridium pincer dihydride electrocatalysts adopted to reduce CO 2 to formates (HCOO − ), exhibiting high efficiency, selectivity and turnover numbers (≈54200), of which mechanism is shown in Figure b.…”

Section: Electrocatalysts For Electrocatalytic Co2 Reductionmentioning

confidence: 99%

Progress and Perspective of Electrocatalytic CO₂ Reduction for Renewable Carbonaceous Fuels and Chemicals

et al. 2017

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The worldwide unrestrained emission of carbon dioxide (CO2) has caused serious environmental pollution and climate change issues. For the sustainable development of human civilization, it is very desirable to convert CO2 to renewable fuels through clean and economical chemical processes. Recently, electrocatalytic CO2 conversion is regarded as a prospective pathway for the recycling of carbon resource and the generation of sustainable fuels. In this review, recent research advances in electrocatalytic CO2 reduction are summarized from both experimental and theoretical aspects. The referred electrocatalysts are divided into different classes, including metal–organic complexes, metals, metal alloys, inorganic metal compounds and carbon‐based metal‐free nanomaterials. Moreover, the selective formation processes of different reductive products, such as formic acid/formate (HCOOH/HCOO−), monoxide carbon (CO), formaldehyde (HCHO), methane (CH4), ethylene (C2H4), methanol (CH3OH), ethanol (CH3CH2OH), etc. are introduced in detail, respectively. Owing to the limited energy efficiency, unmanageable selectivity, low stability, and indeterminate mechanisms of electrocatalytic CO2 reduction, there are still many tough challenges need to be addressed. In view of this, the current research trends to overcome these obstacles in CO2 electroreduction field are summarized. We expect that this review will provide new insights into the further technique development and practical applications of CO2 electroreduction.

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Facilitated carbon dioxide reduction using a Zn(ii) complex

Cited by 34 publications

References 39 publications

Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Electroreduction of CO₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Progress and Perspective of Electrocatalytic CO₂ Reduction for Renewable Carbonaceous Fuels and Chemicals

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Facilitated carbon dioxide reduction using a Zn(ii) complex

Cited by 34 publications

References 39 publications

Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Electroreduction of CO2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Progress and Perspective of Electrocatalytic CO2 Reduction for Renewable Carbonaceous Fuels and Chemicals

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Electroreduction of CO₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Progress and Perspective of Electrocatalytic CO₂ Reduction for Renewable Carbonaceous Fuels and Chemicals