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1.
Proc Natl Acad Sci U S A ; 117(23): 12572-12575, 2020 06 09.
Artigo em Inglês | MEDLINE | ID: mdl-31980521

RESUMO

Electrochemical CO reduction can serve as a sequential step in the transformation of CO2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

2.
Nat Commun ; 11(1): 33, 2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31911585

RESUMO

Electrochemical CO[Formula: see text] reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO[Formula: see text] reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO[Formula: see text] adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO[Formula: see text] adsorption at intermediate ones, and CO[Formula: see text] mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO[Formula: see text] and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.

3.
J Am Chem Soc ; 138(28): 8946-57, 2016 07 20.
Artigo em Inglês | MEDLINE | ID: mdl-27344954

RESUMO

The electrolysis of water to produce hydrogen and oxygen is a simple and attractive approach to store renewable energies in the form of chemical fuels. The oxygen evolution reaction (OER) is a complex four-electron process that constitutes the most energy-inefficient step in water electrolysis. Here we describe a novel electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as OER catalysts. The thin films have nanodomains of crystallinity with lattice spacing similar to those of double-layered hydroxides. The loadings of these thin-film catalysts were accurately determined with a resolution of below 1 µg cm(-2) using an electrochemical quartz microcrystal balance. The loading-activity relations for various catalysts were established using voltammetry and impedance spectroscopy. The thin-film catalysts have up to four types of loading-activity dependence due to film nucleation and growth as well as the resistance of the films. A zone of intrinsic activity has been identified for all of the catalysts where the mass-averaged activity remains constant while the loading is increased. According to their intrinsic activities, the metal oxides can be classified into three categories: NiOx, MnOx, and FeOx belong to category I, which is the least active; CoOx and CoNiOx belong to category II, which has medium activity; and FeNiOx, CoFeOx, and CoFeNiOx belong to category III, which is the most active. The high turnover frequencies of CoFeOx and CoFeNiOx at low overpotentials and the simple deposition method allow the fabrication of high-performance anode electrodes coated with these catalysts. In 1 M KOH and with the most active electrode, overpotentials as low as 240 and 270 mV are required to reach 10 and 100 mA cm(-2), respectively.

4.
J Am Chem Soc ; 137(31): 9927-36, 2015 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-26200221

RESUMO

Sunlight-driven water splitting to produce hydrogen fuel is an attractive method for renewable energy conversion. Tandem photoelectrochemical water splitting devices utilize two photoabsorbers to harvest the sunlight and drive the water splitting reaction. The absorption of sunlight by electrocatalysts is a severe problem for tandem water splitting devices where light needs to be transmitted through the larger bandgap component to illuminate the smaller bandgap component. Herein, we describe a novel method for the deposition of an optically transparent amorphous iron nickel oxide oxygen evolution electrocatalyst. The catalyst was deposited on both thin film and high-aspect ratio nanostructured hematite photoanodes. The low catalyst loading combined with its high activity at low overpotential results in significant improvement on the onset potential for photoelectrochemical water oxidation. This transparent catalyst further enables the preparation of a stable hematite/perovskite solar cell tandem device, which performs unassisted water splitting.

5.
J Am Chem Soc ; 137(22): 7035-8, 2015 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-26005904

RESUMO

Coupling of Earth-abundant hydrogen evolution catalysts to photoabsorbers is crucial for the production of hydrogen fuel using sunlight. In this work, we demonstrate the use of magnetron sputtering to deposit Mo2C as an efficient hydrogen evolution reaction catalyst onto surface-protected amorphous silicon (a-Si) photoabsorbers. The a-Si/Mo2C photocathode evolves hydrogen under simulated solar illumination in strongly acidic and alkaline electrolytes. Onsets of photocurrents are observed at potentials as positive as 0.85 V vs RHE. Under AM 1.5G (1 sun) illumination, the photocathodes reach current densities of -11.2 mA cm(-2) at the reversible hydrogen potential in 0.1 M H2SO4 and 1.0 M KOH. The high photovoltage and low-cost of the Mo2C/a-Si assembly make it a promising photocathode for solar hydrogen production.

6.
Angew Chem Int Ed Engl ; 54(2): 664-7, 2015 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-25403656

RESUMO

The splitting of water into hydrogen and oxygen molecules using sunlight is an attractive method for solar energy storage. Until now, photoelectrochemical hydrogen evolution is mostly studied in acidic solutions, in which the hydrogen evolution is more facile than in alkaline solutions. Herein, we report photoelectrochemical hydrogen production in alkaline solutions, which are more favorable than acidic solutions for the complementary oxygen evolution half-reaction. We show for the first time that amorphous molybdenum sulfide is a highly active hydrogen evolution catalyst in basic medium. The amorphous molybdenum sulfide catalyst and a Ni-Mo catalyst are then deposited on surface-protected cuprous oxide photocathodes to catalyze sunlight-driven hydrogen production in 1 M KOH. The photocathodes give photocurrents of -6.3 mA cm(-2) at the reversible hydrogen evolution potential, the highest yet reported for a metal oxide photocathode using an earth-abundant hydrogen evolution reaction catalyst.

7.
Acc Chem Res ; 47(8): 2671-81, 2014 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-25065612

RESUMO

Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared from simple wet-chemical routes. Electron transport is sometimes slow in the particle catalysts, and an impedance model has been established to identify this slow electron transport. Finally, the amorphous molybdenum sulfide film catalyst has been integrated onto a copper(I) oxide photocathode for photoelectrochemical hydrogen evolution. The conformal catalyst efficiently extracts the excited electrons to give an impressive photocurrent density of -5.7 mA/cm(2) at 0 V vs RHE. The catalyst also confers good stability.

8.
Chem Soc Rev ; 43(18): 6555-69, 2014 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-24626338

RESUMO

Progress in catalysis is driven by society's needs. The development of new electrocatalysts to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks for today's scientists and engineers. The electrochemical splitting of water into hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged. Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches might pave the way for future development of highly efficient catalysts for energy conversion.

9.
Nat Commun ; 5: 3059, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24402352

RESUMO

Concerns over climate change resulting from accumulation of anthropogenic carbon dioxide in the atmosphere and the uncertainty in the amount of recoverable fossil fuel reserves are driving forces for the development of renewable, carbon-neutral energy technologies. A promising clean solution is photoelectrochemical water splitting to produce hydrogen using abundant solar energy. Here we present a simple and scalable technique for the deposition of amorphous molybdenum sulphide films as hydrogen evolution catalyst onto protected copper(I) oxide films. The efficient extraction of excited electrons by the conformal catalyst film leads to photocurrents of up to -5.7 mA cm(-2) at 0 V versus the reversible hydrogen electrode (pH 1.0) under simulated AM 1.5 solar illumination. Furthermore, the photocathode exhibits enhanced stability under acidic environments, whereas photocathodes with platinum nanoparticles as catalyst deactivate more rapidly under identical conditions. The work demonstrates the potential of earth-abundant light-harvesting material and catalysts for solar hydrogen production.

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