CO<sub>2</sub> Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields

Clark, Melissa L.; Ge, Aimin; Videla, Pablo E.; Rudshteyn, Benjamin; Miller, Christopher J.; Song, Jia; Batista, Víctor S.; Lian, Tianquan; Kubiak, Clifford P.

doi:10.1021/jacs.8b09852

Cited by 113 publications

(131 citation statements)

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“…Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations using the Gaussian 2016 software package, revision A.03 (Frisch et al, 2016), were performed to compute optimized structures, frontier orbitals, vibrational frequencies, reduction potentials and UV/Vis spectra. DFT-based SFG spectra were simulated following previously published protocols (Anfuso et al, 2011(Anfuso et al, , 2012Clark et al, 2016Clark et al, , 2018bGe et al, 2016Ge et al, , 2017. Detailed methods are provided in Supplementary Material, including the description of functionals and basis sets.…”

Section: Computational Methodologymentioning

confidence: 99%

“…The optimized structure of ReSS consists of an almost "standing-up" configuration with both sulfur atoms anchored to the gold surface, with sulfur-gold distances of ∼2.6 Å. Such a perpendicular orientation with respect to the surface contrasts with the geometry adopted by the Re complex with a 4-S-2,2 ′ -bipyridine ligand that adopts a tilted orientation unfavorable for substrate binding (Clark et al, 2018b). Instead, the binding mode of ReSS should facilitate CO 2 binding since the active site is left exposed to the solvent instead of being blocked and strongly interacting with the electrode surface.…”

Section: Sum Frequency Generation Spectroscopymentioning

confidence: 97%

“…1 H-NMR spectrum (600 MHz, CD 3 CN) δ 8.89 (2, dd, 2H, J = 5.4, 1.4), 8.06 (4, dd, 2H, J = 8.1, 1.4), 7.56 (3, dd, 2H J = 8.1, 5.4). 13 C-NMR (150 MHz, CD 3 CN) δ 151.89 (Clark et al, 2018a), 127.82 (Schneider et al, 2016), 138.65 (Kaim, 2011), 135.21 (Clark et al, 2018b), 153.51 (Zhanaidarova et al, 2019). ESI-MS (MeOH, m/z):…”

Section: Synthesis [Re(ssbpy)(co) 3 Cl] (Ress)mentioning

confidence: 99%

“…We performed DFT optimizations of the complex on an Au (111) model surface to better understand the binding conformation of the Re complex adsorbed on the gold electrode as compared to previously reported studies of Re complexes on surfaces (Anfuso et al, 2011(Anfuso et al, , 2012Clark et al, 2016Clark et al, , 2018bGe et al, 2016Ge et al, , 2017. Figure 7 shows the lowest-energy minima geometry for both ReSS and ReS complexes (see also Figure S21).…”

Section: Sum Frequency Generation Spectroscopymentioning

confidence: 99%

“…An outstanding challenge is the design of robust anchoring ligands that could stabilize the catalysts on the surface even under sufficiently negative potentials as necessary for catalysis. Functional groups on the bpy ligand can be used to anchor the complexes to surfaces, including thiol groups for gold electrodes and ethynyl groups for carbon electrodes (Clark et al, 2018b;Zhanaidarova et al, 2019). The orientation and properties of molecular catalysts on electrode surfaces can be analyzed by combining vibrational sum-frequency generation (SFG) spectroscopy and computational modeling (Anfuso et al, 2011(Anfuso et al, , 2012Clark et al, 2016Clark et al, , 2018bGe et al, 2016Ge et al, , 2017.…”

Section: Introductionmentioning

confidence: 99%

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Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

et al. 2020

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Heterogenization of homogenous catalysts on electrode surfaces provides a valuable approach for characterization of catalytic processes in operando conditions using surface selective spectroelectrochemistry methods. Ligand design plays a central role in the attachment mode and the resulting functionality of the heterogenized catalyst as determined by the orientation of the catalyst relative to the surface and the nature of specific interactions that modulate the redox properties under the heterogeneous electrode conditions. Here, we introduce new [Re(L)(CO) 3 Cl] catalysts for CO 2 reduction with sulfur-based anchoring groups on a bipyridyl ligand, where L = 3,3 ′-disulfide-2,2 ′-bipyridine (SSbpy) and 3,3 ′-thio-2,2 ′-bipyridine (Sbpy). Spectroscopic and electrochemical analysis complemented by computational modeling at the density functional theory level identify the complex [Re(SSbpy)(CO) 3 Cl] as a multi-electron acceptor that combines the redox properties of both the rhenium tricarbonyl core and the disulfide functional group on the bipyridyl ligand. The first reduction at −0.85 V (vs. SCE) involves a two-electron process that breaks the disulfide bond, activating it for surface attachment. The heterogenized complex exhibits robust anchoring on gold surfaces, as probed by vibrational sum-frequency generation (SFG) spectroscopy. The binding configuration is normal to the surface, exposing the active site to the CO 2 substrate in solution. The attachment mode is thus particularly suitable for electrocatalytic CO 2 reduction.

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Section: Computational Methodologymentioning

confidence: 99%

Section: Sum Frequency Generation Spectroscopymentioning

confidence: 97%

Section: Synthesis [Re(ssbpy)(co) 3 Cl] (Ress)mentioning

confidence: 99%

Section: Sum Frequency Generation Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

et al. 2020

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Engineering Electrochemical Surface for Efficient Carbon Dioxide Upgrade

Wen

Ren

Zheng

et al. 2021

Advanced Energy Materials

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The increasing atmospheric CO 2 raises many associated issues, such as the rise of global mean temperature, the mass loss of polar ice sheets, and subsequent rise of global average sea level, etc. [3] As a result, there is serious motivation to capture and utilize this kind of greenhouse gas [4] and reduce reliance on fossil fuels by utilizing alternative renewable energies to achieve carbon neutrality. [5] Whilst solar and wind renewable energy sources already play an impressively increasing role in the global energy mix, energy storage systems are required to regulate this intermittent and fluctuating renewable electricity. [6] The residual or excess electrical energy from these intermittent sources can therefore be used to transform CO 2 into valuable fuels and chemicals, acting as one class of long-term energy storage. Based on these driving forces, electrocatalytic CO 2 conversion holds great promise as a future technology to store renewable energy in the long term and sequester CO 2 in the earth's carbon cycle. Generally, electrocatalytic CO 2 conversion and upgrade can take place over a wide range of temperatures and/or pressures. [7] The electrochemical CO 2 reduction reaction (CO 2 RR) at ambient temperature/pressure is considered an ideal route and offers significant opportunities to lower the global carbon footprint with wide applications. [8] CO 2 RR has become a prominent research direction, and it is of paramount importance in the electrochemical and carbon chemical industry. This approach creates a sustainable global-scale carbon-neutral economy, [9] allowing for a more innovative carbon capture and utilization (CCU) instead of carbon capture and storage. [10] CO 2 RR has many economic and environmental benefits, which includes, but is not limited to, its capability to i) reduce carbon emission by efficient utilization and conversion of CO 2 , ii) conveniently convert and store surplus intermittent renewable energies, iii) synthesize useable commercial chemicals for new applications, iv) easily regulate reaction rate/selectivity through applied voltages, and v) adapt to a wide-scale process by applications of modular electrolytic cells. [11] As an emerging part of CCU techniques, CO 2 RR provides a promising opportunity to develop new clean technologies to further tackle the issue of global warming.At its current technological state, the development of CO 2 RR is still in its infancy and faces a series of natural barriers. The Electrochemical CO 2 conversion offers an attractive route for recycling CO 2 with economic and environmental benefits, while the catalytic materials and electrode structures still require further improvements for scale-up application. Electrocatalytic surface and near-surface engineering (ESE) has great potential to advance CO 2 reduction reactions (CO 2 RR) with improved activity, selectivity, energetic efficiency, stability, and reduced overpotentials. This review initially provides a panorama of ESE effects to give a clear perspective and leverage their advantages, i...

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Efficient Photocatalytic Selective Oxidation of Benzylamines over Cobalt Molecular Catalyst Covalently Bonded to Carboxyl Functionalized Carbon Nitride

Wang,

Li,

Guo

et al. 2023

Adv Energy and Sustain Res

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Photocatalysis is accepted as a promising method for selective oxidative coupling of amine to imine. However, owing to the rapid dehydrogenation of the generated imine intermediate of α‐amino hydrogen to butyronitrile, it remains a huge challenge to fabricate an exquisite catalyst with enhanced conversion and selectivity. Herein, a novel heterogeneous catalyst (Bpy‐CoCl2/CNCOOH) is developed, where carboxyl functionalized carbon nitride (CNCOOH) serves as a substrate material and couples with highly efficient cobalt‐aminopyridine (Bpy‐CoCl2) molecular catalyst through covalent bonding. The catalyst not only effectively facilitates the transfer of photogenerated charges, but also generates mildly oxidatively active species of superoxide radicals, which can effectively oxidize various functionalized benzylamines to corresponding imines in the presence of oxygen with at least 78.5% conversion and >99% selectivity using O2 as oxygen source, especially for the unmodified benzylamine with >99% conversion and >99% selectivity. This unique combination of a selective molecular catalyst and a simple and robust semiconducting material open new avenues for the selective oxidative coupling of amines.

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CO₂ Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields

Cited by 113 publications

References 120 publications

Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

Engineering Electrochemical Surface for Efficient Carbon Dioxide Upgrade

Efficient Photocatalytic Selective Oxidation of Benzylamines over Cobalt Molecular Catalyst Covalently Bonded to Carboxyl Functionalized Carbon Nitride

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CO2 Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields

Cited by 113 publications

References 120 publications

Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

Robust Binding of Disulfide-Substituted Rhenium Bipyridyl Complexes for CO2 Reduction on Gold Electrodes

Engineering Electrochemical Surface for Efficient Carbon Dioxide Upgrade

Efficient Photocatalytic Selective Oxidation of Benzylamines over Cobalt Molecular Catalyst Covalently Bonded to Carboxyl Functionalized Carbon Nitride

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CO₂ Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields