Reversible and Selective Interconversion of Hydrogen and Carbon Dioxide into Formate by a Semiartificial Formate Hydrogenlyase Mimic

Sokol, Katarzyna P.; Robinson, William E.; Oliveira, Ana Rita; Zacarias, Sónia; Lee, Chong; Madden, Christopher; Bassegoda, Arnau; Hirst, Judy; Pereira, Inês; Reisner, Erwin

doi:10.1021/jacs.9b09575

Cited by 38 publications

(30 citation statements)

References 39 publications

(82 reference statements)

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“…Heating the reaction mixture to 60 °C followed by cooling to room temperature has afforded a deep purple coloured coordination polymer gel (Zn-TPY-TTF CPG) ( Fig. 2a, Supplementary Figs. [11][12][13][14].…”

Section: Resultsmentioning

confidence: 99%

“…9,10 The synthetic assimilation of these parameters precisely in a spatial organization of molecular components is indeed a challenging task. [11][12][13][14] The recent upsurge of converting CO 2 into fuels like CH 3 OH, CH 4, or different chemical feedstock has gained widespread attention. [15][16][17][18][19] The conversion of CO 2 to hydrocarbon fuels would mitigate not only the effect of CO 2 concentration in the atmosphere but also reduce the dependency on fossil fuel-based economy.…”

Section: Introductionmentioning

confidence: 99%

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Charge-Transfer Regulated Visible Light Driven Photocatalytic H2 Production and CO2 Reduction in Tetrathiafulvalene Based Coordination Polymer Gel

Verma¹,

Sarkar²,

Singh³

et al. 2020

Preprint

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The much-needed renewable alternatives to fossil fuel can be achieved efficiently and sustainably by converting solar energy to solar fuels via hydrogen generation from water or CO2 reduction. In this regard, a soft processable metal-organic hybrid semiconducting material has been developed and studied for photocatalytic activity towards H2 production and CO2 reduction to CO and CH4 under visible light and direct sunlight irradiation. A tetrapodal low molecular weight gelator is synthesized by integrating tetrathiafulvalene and terpyridine through amide linkage (TPY-TTF). The TPY-TTF acts as a linker and by self-assembly with ZnII results in a charge-transfer (CT) coordination polymer gel (CPG); Zn-TPY-TTF. The Zn-TPY-TTF shows impressive photocatalytic activity towards H2 production (rate = 530 μmol g-1h-1) and CO2 reduction to CO (rate = 438 μmol g-1h-1, selectivity >99%) regulated by charge-transfer interaction. Furthermore, in-situ stabilization of Pt nanoparticles to CPG (Pt@Zn-TPY-TTF) exhibits remarkably enhanced H2 evolution (rate =14727 μmol g-1h-1). Importantly, Pt@Zn-TPY-TTF modulate the CO2 reduction from CO to CH4 (rate = 292 μmol g-1h-1, selectivity >97%). Real-time CO2 reduction reaction is monitored by in-situ DRIFT study and subsequent plausible mechanism is derived computationally. The photocatalytic activity of Zn-TPY-TTF and Pt@Zn-TPY-TTF composite was also examined under sunlight that display excellent H2 evolution and CO2 reduction.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Charge-Transfer Regulated Visible Light Driven Photocatalytic H2 Production and CO2 Reduction in Tetrathiafulvalene Based Coordination Polymer Gel

Verma¹,

Sarkar²,

Singh³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

“…H 2 ase and Fdh from E. coli were wired to macro‐mesoporous IO‐ITO anode and cathode respectively. Both electrodes maintained good activity after 24 h for both oxidation and reduction and FEs for HCOO − and H 2 production were determined to be 76 % and 77 % respectively …”

Section: Recent Examples Of Enzymatic Electrochemistry For Small Molementioning

confidence: 96%

“…The electrons from H 2 oxidation are then transferred to the cathode for the reduction of substrates (such as N 2 , O 2 , CO 2 , etc .) . Also, H 2 ases have been deeply studied by electrochemistry since the 1980s for mechanistic studies .…”

Section: Recent Examples Of Enzymatic Electrochemistry For Small Molementioning

confidence: 99%

Recent Enzymatic Electrochemistry for Reductive Reactions

Cadoux

Milton

2020

ChemElectroChem

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Enzymatic electrochemistry is the coupling of oxidoreductase enzymes to electrodes, where electrons are transferred between the electrode and an enzyme's cofactor(s). In addition to enzymatic electrochemistry enabling mechanistic study [such as the determination of cofactor reduction potential(s)], enzymatic electrocatalysis also enables substrate reduction or oxidation by exploiting the catalytic properties of enzymes. This Minireview illustrates some recent examples, in which electrodes are coupled with enzymes that catalyze the reduction of substrates such as dinitrogen (N 2 ), carbon dioxide (CO 2 ) and protons (H + ), performed by metalloenzymes such as nitrogenases, formate dehydrogenases and hydrogenases. We review some strategies to achieve electron transfer (such as mediated and direct electron transfer), as well as some key results of recent studies.

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“…Recently, the high activity of FDHs has motivated their incorporation into colloidal and electrochemical devices capable of efficient light-driven CO 2 reduction, 12 − 16 into enzymatic formate fuel cells, 17 and into semi-artificial mimics of formate hydrogenlyase systems. 18 These systems often function with high thermodynamic efficiency, enabled by FDH electrocatalysis.…”

Section: Introductionmentioning

confidence: 99%

Understanding How the Rate of C–H Bond Cleavage Affects Formate Oxidation Catalysis by a Mo-Dependent Formate Dehydrogenase

et al. 2020

Self Cite

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Metal-dependent formate dehydrogenases (FDHs) catalyze the reversible conversion of formate into CO 2 , a proton, and two electrons. Kinetic studies of FDHs provide key insights into their mechanism of catalysis, relevant as a guide for the development of efficient electrocatalysts for formate oxidation as well as for CO 2 capture and utilization. Here, we identify and explain the kinetic isotope effect (KIE) observed for the oxidation of formate and deuterioformate by the Mo-containing FDH from Escherichia coli using three different techniques: steady-state solution kinetic assays, protein film electrochemistry (PFE), and pre-steady-state stopped-flow methods. For each technique, the Mo center of FDH is reoxidized at a different rate following formate oxidation, significantly affecting the observed kinetic behavior and providing three different viewpoints on the KIE. Steady-state turnover in solution, using an artificial electron acceptor, is kinetically limited by diffusional intermolecular electron transfer, masking the KIE. In contrast, interfacial electron transfer in PFE is fast, lifting the electron-transfer rate limitation and manifesting a KIE of 2.44. Pre-steady-state analyses using stopped-flow spectroscopy revealed a KIE of 3 that can be assigned to the C–H bond cleavage step during formate oxidation. We formalize our understanding of FDH catalysis by fitting all the data to a single kinetic model, recreating the condition-dependent shift in rate-limitation of FDH catalysis between active-site chemical catalysis and regenerative electron transfer. Furthermore, our model predicts the steady-state and time-dependent concentrations of catalytic intermediates, providing a valuable framework for the design of future mechanistic experiments.

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Reversible and Selective Interconversion of Hydrogen and Carbon Dioxide into Formate by a Semiartificial Formate Hydrogenlyase Mimic

Cited by 38 publications

References 39 publications

Charge-Transfer Regulated Visible Light Driven Photocatalytic H2 Production and CO2 Reduction in Tetrathiafulvalene Based Coordination Polymer Gel

Charge-Transfer Regulated Visible Light Driven Photocatalytic H2 Production and CO2 Reduction in Tetrathiafulvalene Based Coordination Polymer Gel

Recent Enzymatic Electrochemistry for Reductive Reactions

Understanding How the Rate of C–H Bond Cleavage Affects Formate Oxidation Catalysis by a Mo-Dependent Formate Dehydrogenase

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