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1.
ACS Appl Mater Interfaces ; 12(5): 5251-5258, 2020 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-31971360

RESUMO

Conversion of CO2 to reduced products is a promising route to alleviate irreversible climate change. Here we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ∼90% for CO at 490 mV of overpotential (-0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at -0.7 V versus RHE surpasses other Co-based molecular and metal-organic framework catalysts for CO2 reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO2 adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO2 conversion. Our study shows that CoPc-Pyr reduces CO2 at lower overpotential and with higher activity than noble metal electrodes, such as silver.

2.
J Am Chem Soc ; 141(10): 4191-4193, 2019 03 13.
Artigo em Inglês | MEDLINE | ID: mdl-30798595

RESUMO

The electrochemical reduction of CO and CO2 over Cu produces a variety of multicarbon products. Interestingly, recent isotope experiments have suggested that the oxygen atoms contained in the multicarbon alcohols produced over Cu are derived from solvent water. This observation has brought into question many of the proposed reaction mechanisms by which these multicarbon alcohols are produced over Cu. However, these surprising experimental observations are likely the result of isotopic scrambling between transiently produced carbonyl-containing intermediate reaction products, such as acetaldehyde, with solvent water and not another mechanism. The existence of such carbonyl-containing intermediate reaction products is supported by both experimental and theoretical studies. Furthermore, theoretical calculations support the notion that the reversible hydration of these carbonyl-containing species is facile in the vicinity of the Cu surface.

3.
Phys Chem Chem Phys ; 21(10): 5402-5408, 2019 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-30785434

RESUMO

The rational improvement of current and developing electrochemical technologies requires atomistic understanding of electrode-electrolyte interfaces. However, examining these interfaces under operando conditions, where performance is typically evaluated and benchmarked, remains challenging, as it necessitates incorporating an operando probe during full electrochemical operation. In this study, we describe a custom electrochemical flow cell that enables near-surface-sensitive operando investigation of planar thin-film catalysts at significant hydrogen evolution reaction (HER) rates (in excess of -100 mA cm-2) using grazing incidence X-ray methods. Grazing-incidence X-ray spectroscopy and diffraction were implemented on the same sample under identical HER conditions, demonstrating how the combined measurements track changing redox chemistry and structure of Cu thin-film catalyst surfaces as a function of electrochemical conditions. The coupling of these methods with improved mass transport and hydrodynamic control establishes a new paradigm for operando measurement design, enabling unique insights into the key fundamental processes occurring at the catalyst-electrolyte interface.

4.
J Am Chem Soc ; 140(27): 8569-8577, 2018 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-29909616

RESUMO

The ability to predict and control the formation of bimetallic heterogeneous nanocrystals is desirable for many applications in plasmonics and catalysis. Here, we report the synthesis and characterization of stable, monodisperse, and solution-processed Cu-Ag bimetallic nanoparticles with specific but unusual elemental arrangements that are consistent with a recently developed thermodynamic model. Using air-free scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy, the distribution of Cu and Ag positions was unambiguously identified within individual nanocrystals (NCs), leading to the discovery of a Cu-Ag nanocrescent shape. A simple yet versatile thermodynamic model was applied to illustrate how the interplay between surface and interface energies determines the particle morphology. It is found that there exists a range of surface-to-interface energy ratios under which crescent-shaped nanocrystals are the thermodynamically favored products, with the morphology tunable by adjusting the Ag content. We further show the conversion of Cu-Ag nanocrescents into Ag@Cu2O upon mild oxidation, whereas fully core-shell Cu@Ag NCs are robust against oxidation up to 100 °C. The plasmonic and interband absorptions of Cu-Ag NCs depend on the composition and the degree of Cu oxidation, which may find application in light-driven catalysis.

5.
J Am Chem Soc ; 140(22): 7012-7020, 2018 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-29756446

RESUMO

The electrochemical reduction of carbon dioxide is sensitive to electrolyte polarization, which causes gradients in pH and the concentration of carbon dioxide to form near the cathode surface. It is desirable to measure the concentration of reaction-relevant species in the immediate vicinity of the cathode because the intrinsic kinetics of carbon dioxide reduction depend on the composition of the local reaction environment. Meeting this objective has proven difficult because conventional analytical methods only sample products from the bulk electrolyte. In this study, we describe the use of differential electrochemical mass spectrometry to measure the concentration of carbon dioxide and reaction products in the immediate vicinity of the cathode surface. This capability is achieved by coating the electrocatalyst directly onto the pervaporation membrane used to transfer volatile species into the mass spectrometer, thereby enabling species to be sampled directly from the electrode-electrolyte interface. This approach has been used to investigate hydrogen evolution and carbon dioxide reduction over Ag and Cu. We find that the measured CO2 reduction activity of Ag agrees well with what is measured by gas chromatography of the effluent from an H-cell operated with the same catalyst and electrolyte. A distinct advantage of our approach is that it enables observation of the depletion of carbon dioxide near the cathode surface due to reaction with hydroxyl anions evolved at the cathode surface, something that cannot be done using conventional analytical techniques. We also demonstrate that the influence of this relatively slow chemical reaction can be minimized by evaluating electrocatalytic activity during a rapid potential sweep, thereby enabling measurement of the intrinsic kinetics. For CO2 reduction over Cu, nine products can be observed simultaneously in real time. A notable finding is that the abundance of aldehydes relative to alcohols near the cathode surface is much higher than that observed in the bulk electrolyte. It is also observed that for increasingly cathodic potentials the relative abundance of ethanol increases at the expense of propionaldehyde. These findings suggest that acetaldehyde is a precursor to ethanol and propionaldehyde and that propionaldehyde is a precursor to n-propanol.

6.
J Am Chem Soc ; 139(44): 15848-15857, 2017 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-28988474

RESUMO

The electrochemical reduction of carbon dioxide using renewably generated electricity offers a potential means for producing fuels and chemicals in a sustainable manner. To date, copper has been found to be the most effective catalyst for electrochemically reducing carbon dioxide to products such as methane, ethene, and ethanol. Unfortunately, the current efficiency of the process is limited by competition with the relatively facile hydrogen evolution reaction. Since multi-carbon products are more valuable precursors to chemicals and fuels than methane, there is considerable interest in modifying copper to enhance the multi-carbon product selectivity. Here, we report our investigations of electrochemical carbon dioxide reduction over CuAg bimetallic electrodes and surface alloys, which we find to be more selective for the formation of multi-carbon products than pure copper. This selectivity enhancement is a result of the selective suppression of hydrogen evolution, which occurs due to compressive strain induced by the formation of a CuAg surface alloy. Furthermore, we report that these bimetallic electrocatalysts exhibit an unusually high selectivity for the formation of multi-carbon carbonyl-containing products, which we hypothesize to be the consequence of a reduced coverage of adsorbed hydrogen and the reduced oxophilicity of the compressively strained copper. Thus, we show that promoting copper surface with small amounts of Ag is a promising means for improving the multi-carbon oxygenated product selectivity of copper during electrochemical CO2 reduction.

7.
Chem Commun (Camb) ; 53(79): 10870-10873, 2017 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-28875996

RESUMO

The synthesis of high surface-area colloidal assemblies of calixarene-phosphine-capped nanoporous gold is reported under reductive electrochemical conditions. These materials uniquely exhibit a remarkably thin wall thickness down to 10 nm, while possessing pore sizes on the order of up to hundreds of nanometers, which can be controlled via choice of organic ligand.

8.
Proc Natl Acad Sci U S A ; 112(45): E6111-8, 2015 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-26504215

RESUMO

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

9.
Anal Chem ; 87(15): 8013-20, 2015 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-26153829

RESUMO

The discovery of electrocatalysts that can efficiently reduce CO2 to fuels with high selectivity is a subject of contemporary interest. Currently, the available analytical methods for characterizing the products of CO2 reduction require tens of hours to obtain the dependence of product distribution on applied potential. As a consequence, there is a need to develop novel analytical approaches that can reduce this analysis time down to about an hour. We report here the design, construction, and operation of a novel differential electrochemical mass spectrometer (DEMS) cell geometry that enables the partial current densities of volatile electrochemical reaction products to be quantified in real time. The capabilities of the novel DEMS cell design are demonstrated by carrying out the electrochemical reduction of CO2 over polycrystalline copper. The reaction products are quantified in real time as a function of the applied potential during linear sweep voltammetry, enabling the product spectrum produced by a given electrocatalyst to be determined as a function of applied potential on a time scale of roughly 1 h.

10.
Phys Chem Chem Phys ; 17(29): 18924-36, 2015 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-26103939

RESUMO

Solar-driven electrochemical cells can be used to convert carbon dioxide, water, and sunlight into transportation fuels or into precursors to such fuels. The voltage efficiency of such devices depends on the (i) physical properties of its components (catalysts, electrolyte, and membrane); (ii) operating conditions (carbon dioxide flowrate and pressure, current density); and (iii) physical dimensions of the cell. The sources of energy loss in a carbon dioxide reduction (CO2R) cell are the anode and cathode overpotentials, the difference in pH between the anode and cathode, the difference in the partial pressure of carbon dioxide between the bulk electrolyte and the cathode, the ohmic loss across the electrolyte and the diffusional resistances across the boundary layers near the electrodes. In this study, we analyze the effects of these losses and propose optimal device configurations for the efficient operation of a CO2R electrochemical cell operating at a current density of 10 mA cm(-2). Cell operation at near-neutral bulk pH offers not only lower polarization losses but also better selectivity to CO2R versus hydrogen evolution. Addition of supporting electrolyte to increase its conductivity has a negative impact on cell performance because it reduces the electric field and the solubility of CO2. Addition of a pH buffer reduces the polarization losses but may affect catalyst selectivity. The carbon dioxide flowrate and partial pressure can have severe effects on the cell efficiency if the carbon dioxide supply rate falls below the consumption rate. The overall potential losses can be reduced by use of an anion, rather than a cation, exchange membrane. We also show that the maximum polarization losses occur for the electrochemical synthesis of CO and that such losses are lower for the synthesis of products requiring a larger number of electrons per molecule, assuming a fixed current density. We also find that the reported electrocatalytic activity of copper below -1 V vs. RHE is strongly influenced by excessive polarization of the cathode and, hence, does not represent its true activity at bulk conditions. This article provides useful guidelines for minimizing polarization losses in solar-driven CO2R electrochemical cells and a method for predicting polarization losses and obtaining kinetic overpotentials from measured partial current densities.

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