Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

Nam, Dong Heon; Zhang, Jenny; Andrei, Virgil; Kornienko, Nikolay; Heidary, Nina; Wagner, Andreas; Nakanishi, Kenichi; Sokol, Katarzyna P.; Slater, Barnaby; Zebger, Ingo; Hofmann, Stephan; Fontecilla‐Camps, Juan C.; Park, Chan Beum; Reisner, Erwin

doi:10.1002/anie.201805027

Cited by 96 publications

(91 citation statements)

References 34 publications

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“…As the most selective polymer toward CO production, P2 1 was immobilized on a p ‐type Si (Si) semiconductor electrode for photoelectrochemical CO 2 reduction. This was enabled by interfacing a compatible IO‐TiO 2 layer with light‐harvesting Si as previously reported . Linear sweep voltammograms under chopped illumination were conducted on the Si|IO‐TiO 2 | P2 1 photocathode in the same electrolyte solution as that used for the Ti|IO‐TiO 2 | P2 1 cathodes (Supporting Information, Figure S19a).…”

Section: Figuresupporting

confidence: 87%

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

et al. 2019

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As eries of copolymers comprising at erpyridine ligand and various functional groups were synthesized toward integrating aC o-based molecular CO 2 reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules,t he Co-coordinated polymers were readily immobilizedv ia phosphonate anchoring groups.W ithin the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO 2 reduction selectivity in the presence of water.E lectrochemical and photoelectrochemical CO 2 reduction were demonstrated with the polymer-immobilized hybrid cathodes,with aCO:H 2 product ratio of up to 6:1 compared to 2:1f or ac orresponding "monomeric" Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer-sphere environment of synthetic molecular catalysts,a nalogous to CO 2 reductases.Electrocatalytic reduction of CO 2 selectively to CO remains am ajor goal toward realizing as ustainable,c losed carbon cycle. [1] To this end, molecular catalysts have been developed taking inspiration from natural archetypes such as CO and formate dehydrogenase enzymes. [2] While still dominated by precious metal-based complexes,t remendous efforts have recently been devoted to designing earth-abundant 3d transition metal-based catalysts. [3] Often limited by their low stability and solubility,aswell as the low concentration of CO 2 and competing H 2 evolution in water, examples of first-row transition metals performing aqueous CO 2 reduction remain scarce.Since early reports of Ni cyclam [4] and LehnsR e [5] catalysts,o ptimizing molecular design toward improved product selectivity has principally involved tailoring the metalsprimary coordination sphere. [3] Alternative strategies have incorporated catalysts almost exclusively with carbon materials to provide hybrid electrodes with ah ydrophobic environment conducive to CO 2 utilization, even in water. [6] Considering their facile preparation and stability in water, metal oxides represent an alternative class of promising materials,a nd have been successfully exploited both in photocatalytic colloidal schemes and as cathode substrates toward H 2 evolution. [7] However,t heir hydrophilicity and propensity toward hydrogen bonding generally promote H 2 evolution over CO 2 reduction.Herein we report rationally designed polymers for selective CO production and their incorporation into porous electrode architectures to produce precious metal-free CO 2 reduction cathodes.B uilding upon our recent utilization of ap hosphonated Co bis(tpy) catalyst (tpy = 2,2':6',2''-terpyridine), CotpyP (see the Supporting Information), toward photoelectrochemical reduction of CO 2 in aqueous environments, [8] we demonstrate that integrating the CO 2 reduction catalyst in ar ationally designed copolymer is ap romising strategy for engineering the outer-sphere environment around the metal center to achieve improved CO 2 reduction performance. [2a, 9] Copolymer scaffold...

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Section: Figuresupporting

confidence: 87%

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

et al. 2019

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“…This was enabled by interfacing ac ompatible IO-TiO 2 layer with light-harvesting Si as previously reported. [18] Linear sweep voltammograms under chopped illumination were conducted on the Si j IO-TiO 2 j P2 1 photocathode in the same electrolyte solution as that used for the Ti j IO-TiO 2 j P2 1 cathodes (Supporting Information, Figure S19a). Ap hotocurrent onset at À0.5 Vv s. Fc + /Fc 0 and density of À450 mAcm À2 at À1.0 V vs.F c + /Fc 0 were observed, which compares favorably to the À150 mAcm À2 achieved by apolymer-free Si j IO-TiO 2 control electrode.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Ap hotocurrent onset at À0.5 Vv s. Fc + /Fc 0 and density of À450 mAcm À2 at À1.0 V vs.F c + /Fc 0 were observed, which compares favorably to the À150 mAcm À2 achieved by apolymer-free Si j IO-TiO 2 control electrode. [18] Controlled potential photoelectrolysis at À1.0 V vs.F c + /Fc 0 under irradiation (100 mW cm À2 ,A M1.5 G, l > 400 nm) on the Si j IO-TiO 2 j P2 1 electrode produced CO at about 80 %product selectivity over 6h(Supporting Information, Figure S19b,c). Thelow FE is coherent with the electrocatalysis results and highlights the need for am ore inert or conductive polymer backbone and/or more efficient electron transfer between the surface and the polymer.N either the catalyst-free Si j IO-TiO 2 photoelectrode under CO 2 nor Si j IO-TiO 2 j P2 1 under N 2 produced detectable amounts of CO or H 2 (Supporting Information, Figure S19b).…”

Section: Angewandte Chemiementioning

confidence: 99%

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

et al. 2019

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A series of copolymers comprising a terpyridine ligand and various functional groups were synthesized toward integrating a Co‐based molecular CO2 reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules, the Co‐coordinated polymers were readily immobilized via phosphonate anchoring groups. Within the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO2 reduction selectivity in the presence of water. Electrochemical and photoelectrochemical CO2 reduction were demonstrated with the polymer‐immobilized hybrid cathodes, with a CO:H2 product ratio of up to 6:1 compared to 2:1 for a corresponding “monomeric” Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer‐sphere environment of synthetic molecular catalysts, analogous to CO2 reductases.

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“…Thei nteraction of FDH and TiO 2 was quantitatively investigated with apreviously described QCM cell. [18,19] Upon flowing an FDH-containing solution over a planarTiO 2covered quartz chip (12 nm in 100 mm TEOA), the surface of TiO 2 reached saturation after 1h,r esulting in approximately 3.5 pmol cm À2 of adsorbed FDH (planarTiO 2 j FDH, Figure 3A). Thestrength of the enzyme-TiO 2 interaction was…”

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Interfacing Formate Dehydrogenase with Metal Oxides for the Reversible Electrocatalysis and Solar‐Driven Reduction of Carbon Dioxide

et al. 2019

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The integration of enzymes with synthetic materials allows efficient electrocatalysis and production of solar fuels. Here, we couple formate dehydrogenase ( FDH ) from Desulfovibrio vulgaris Hildenborough (DvH) to metal oxides for catalytic CO 2 reduction and report an in‐depth study of the resulting enzyme–material interface. Protein film voltammetry (PFV) demonstrates the stable binding of FDH on metal‐oxide electrodes and reveals the reversible and selective reduction of CO 2 to formate. Quartz crystal microbalance (QCM) and attenuated total reflection infrared (ATR‐IR) spectroscopy confirm a high binding affinity for FDH to the TiO 2 surface. Adsorption of FDH on dye‐sensitized TiO 2 allows for visible‐light‐driven CO 2 reduction to formate in the absence of a soluble redox mediator with a turnover frequency (TOF) of 11±1 s −1 . The strong coupling of the enzyme to the semiconductor gives rise to a new benchmark in the selective photoreduction of aqueous CO 2 to formate.

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Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

Cited by 96 publications

References 34 publications

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Interfacing Formate Dehydrogenase with Metal Oxides for the Reversible Electrocatalysis and Solar‐Driven Reduction of Carbon Dioxide

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Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

Cited by 96 publications

References 34 publications

Rational Design of Polymers for Selective CO2 Reduction Catalysis

Rational Design of Polymers for Selective CO2 Reduction Catalysis

Rational Design of Polymers for Selective CO2 Reduction Catalysis

Interfacing Formate Dehydrogenase with Metal Oxides for the Reversible Electrocatalysis and Solar‐Driven Reduction of Carbon Dioxide

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Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Rational Design of Polymers for Selective CO₂ Reduction Catalysis