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1.
Chemphyschem ; 25(13): e202400098, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38546734

RESUMO

The direct conversion of methane into alcohol is a promising approach for achieving a low-carbon future, yet it remains a major challenge. In this study, we utilize density functional theory to explore the potential of the (CoCrFeMnNi)3O4 (CCFMNO) high entropy oxide (HEO) for electrochemical oxidation of methane to methanol and ethanol, alongside their competition with CO2 production. Our primary focus in this study is on thermodynamics, enabling a prompt analysis of the catalyst's potential, with the calculation of electrochemical barriers falling beyond our scope. Among all potential active sites within CCFMNO HEO, we identify Co as the most active site for methane activation when using carbonate ions as oxidants. This results in methanol production with a limiting potential of 1.4 VCHE, and ethanol and CO2 productions with a limiting potential of 1.2 VCHE. Additionally, our findings suggest that the occupied p-band center of O* on CCFMNO HEO is a potential descriptor for identifying the most active site within CCFMNO HEO. Overall, our results indicate that CCFMNO HEO holds promise as catalysts for methane oxidation to alcohols, employing carbonate ions as oxidants.

2.
Adv Sci (Weinh) ; 10(31): e2301912, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37740423

RESUMO

The direct conversion of gaseous methane to energy-dense liquid derivatives such as methanol and ethanol is of profound importance for the more efficient utilization of natural gas. However, the thermo-catalytic partial oxidation of this simple alkane has been a significant challenge due to the high C-H bond energy. Exploiting electrocatalysis for methane activation via active oxygen species generated on the catalyst surface through electrochemical water oxidation is generally considered as economically viable and environmentally benign compared to energy-intensive thermo-catalysis. Despite recent progress in electrochemical methane oxidation to alcohol, the competing oxygen evolution reaction (OER) still impedes achieving high faradaic efficiency and product selectivity. In this review, an overview of current progress in electrochemical methane oxidation, focusing on mechanistic insights on methane activation, catalyst design principles based on descriptors, and the effect of reaction conditions on catalytic performance are provided. Mechanistic requirements for high methanol selectivity, and limitations of using water as the oxidant are discussed, and present the perspective on how to overcome these limitations by employing carbonate ions as the oxidant.

3.
Adv Mater ; 35(18): e2207765, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36773328

RESUMO

While core-shell nanomaterials are highly desirable for realizing enhanced optical and catalytic properties, their synthesis with atomic-level control is challenging. Here, the synthesis and crystal structure of [Au12 Ag32 (SePh)30 ]4- , the first example of selenolated Au-Ag core-shell nanoclusters, comprising a gold icosahedron core trapped in a silver dodecahedron, which is protected by an Ag12 (SePh)30 shell, is presented. The gold core strongly modifies the overall electronic structure and induces synergistic effects, resulting in high enhancements in the stability and near-infrared-II photoluminescence. The Au12 Ag32 and its homometal analog Ag44 , show strong interactions with oxygen vacancies of TiO2 , facilitating the interfacial charge transfer for photocatalysis. Indeed, the Au12 Ag32 /TiO2 exhibits remarkable solar H2 production (6810 µmol g-1  h-1 ), which is ≈6.2 and ≈37.8 times higher than that of Ag44 /TiO2 and TiO2 , respectively. Good stability and recyclability with minimal catalytic activity loss are additional features of Au12 Ag32 /TiO2 . The experimental and computational results reveal that the Au12 Ag32 acts as an efficient cocatalyst by possessing a favorable electronic structure that aligns well with the TiO2 bands for the enhanced separation of photoinduced charge carriers due to the relatively negatively charged Au12 core. These atomistic insights will motivate uncovering of the structure-catalytic activity relationships of other nanoclusters.

4.
J Am Chem Soc ; 145(4): 2152-2160, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36657026

RESUMO

Electrocatalytic CO2 reduction reaction (CO2RR) is greatly facilitated by Au surfaces. However, large fractions of underlying Au atoms are generally unused during the catalytic reaction, which limits mass activity. Herein, we report a strategy for preparing efficient electrocatalysts with high mass activities by the atomic-level transplantation of Au active sites into a Ni4 nanocluster (NC). While the Ni4 NC exclusively produces H2, the Au-transplanted NC selectively produces CO over H2. The origin of the contrasting selectivity observed for this NC is investigated by combining operando and theoretical studies, which reveal that while the Ni sites are almost completely blocked by the CO intermediate in both NCs, the Au sites act as active sites for CO2-to-CO electroreduction. The Au-transplanted NC exhibits a remarkable turnover frequency and mass activity for CO production (206 molCO/molNC/s and 25,228 A/gAu, respectively, at an overpotential of 0.32 V) and high durability toward the CO2RR over 25 h.

5.
J Chem Phys ; 155(1): 014305, 2021 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-34241411

RESUMO

Syngas, a gaseous mixture of CO and H2, is a critical industrial feedstock for producing bulk chemicals and synthetic fuels, and its production via direct CO2 electroreduction in aqueous media constitutes an important step toward carbon-negative technologies. Herein, we report controlled syngas production with various H2/CO ratios via the electrochemical CO2 reduction reaction (CO2RR) on specifically formulated Au25 and PtAu24 nanoclusters (NCs) with core-atom-controlled selectivities. While CO was predominantly produced from the CO2RR on the Au NCs, H2 production was favored on the PtAu24 NCs. Density functional theory calculations of the free energy profiles for the CO2RR and hydrogen evolution reaction (HER) indicated that the reaction energy for the conversion of CO2 to CO was much lower than that for the HER on the Au25 NC. In contrast, the energy profiles calculated for the HER indicated that the PtAu24 NCs have nearly thermoneutral binding properties; thus, H2 production is favored over CO formation. Based on the distinctly different catalytic selectivities of Au25 and PtAu24 NCs, controlled syngas production with H2/CO ratios of 1 to 4 was demonstrated at a constant applied potential by simply mixing the Au25 and PtAu24 NCs based on their intrinsic catalytic activities for the production of CO and H2.

6.
Angew Chem Int Ed Engl ; 60(26): 14563-14570, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-33877721

RESUMO

Accurate identification of active sites is critical for elucidating catalytic reaction mechanisms and developing highly efficient and selective electrocatalysts. Herein, we report the atomic-level identification of active sites using atomically well-defined gold nanoclusters (Au NCs) Au25 , Au38 , and Au144 as model catalysts in the electrochemical CO2 reduction reaction (CO2 RR). The studied Au NCs exhibited remarkably high CO2 RR activity, which increased with increasing NC size. Electrochemical and X-ray photoelectron spectroscopy analyses revealed that the Au NCs were activated by removing one thiolate group from each staple motif at the beginning of CO2 RR. In addition, density functional theory calculations revealed higher charge densities and upshifts of d-states for dethiolated Au sites. The structure-activity properties of the studied Au NCs confirmed that dethiolated Au sites were the active sites and that CO2 RR activity was determined by the number of active sites on the cluster surface.

7.
J Am Chem Soc ; 143(14): 5386-5395, 2021 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-33725440

RESUMO

Pd is one of the most effective catalysts for the electrochemical reduction of CO2 to formate, a valuable liquid product, at low overpotential. However, the intrinsically high CO affinity of Pd makes the surface vulnerable to CO poisoning, resulting in rapid catalyst deactivation during CO2 electroreduction. Herein, we utilize the interaction between metals and metal-organic frameworks to synthesize atomically dispersed Au on tensile-strained Pd nanoparticles showing significantly improved formate production activity, selectivity, and stability with high CO tolerance. We found that the tensile strain stabilizes all reaction intermediates on the Pd surface, whereas the atomically dispersed Au selectively destabilizes CO* without affecting other adsorbates. As a result, the conventional COOH* versus CO* scaling relation is broken, and our catalyst exhibits 26- and 31-fold enhancement in partial current density and mass activity toward electrocatalytic formate production with over 99% faradaic efficiency, compared to Pd/C at -0.25 V versus RHE.

8.
Nat Mater ; 19(4): 436-442, 2020 04.
Artigo em Inglês | MEDLINE | ID: mdl-31932671

RESUMO

Despite the growing demand for hydrogen peroxide it is almost exclusively manufactured by the energy-intensive anthraquinone process. Alternatively, H2O2 can be produced electrochemically via the two-electron oxygen reduction reaction, although the performance of the state-of-the-art electrocatalysts is insufficient to meet the demands for industrialization. Interestingly, guided by first-principles calculations, we found that the catalytic properties of the Co-N4 moiety can be tailored by fine-tuning its surrounding atomic configuration to resemble the structure-dependent catalytic properties of metalloenzymes. Using this principle, we designed and synthesized a single-atom electrocatalyst that comprises an optimized Co-N4 moiety incorporated in nitrogen-doped graphene for H2O2 production and exhibits a kinetic current density of 2.8 mA cm-2 (at 0.65 V versus the reversible hydrogen electrode) and a mass activity of 155 A g-1 (at 0.65 V versus the reversible hydrogen electrode) with negligible activity loss over 110 hours.

9.
Angew Chem Int Ed Engl ; 57(46): 15045-15050, 2018 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-30134041

RESUMO

Methanol is a major fuel and chemical feedstock currently produced from syngas, a CO/CO2 /H2 mixture. Herein we identify formate binding strength as a key parameter limiting the activity and stability of known catalysts for methanol synthesis in the presence of CO2 . We present a molybdenum phosphide catalyst for CO and CO2 reduction to methanol, which through a weaker interaction with formate, can improve the activity and stability of methanol synthesis catalysts in a wide range of CO/CO2 /H2 feeds.

10.
J Phys Chem Lett ; 9(7): 1473-1479, 2018 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-29510623

RESUMO

Density functional theory is employed to investigate the electronic origin and feasibility of surface lattice oxygen (Osurf) participation during the oxygen evolution reaction (OER) on perovskites. Osurf participation occurs via the nonelectrochemical pathway in which adsorbed atomic oxygen (O*) diffuses from the transition-metal site to the oxygen site, and then Osurf shifts out of the surface plane to react with O* to form Osurf-O* and a surface oxygen vacancy. The different thermodynamic driving forces of Osurf participation on LaMO3-δ (M = Ni, Co, and Cu) are explained by the changes in the oxidation state of the transition-metal site throughout the reaction. We show that Osurf participation on LaNiO3 cannot be hindered by Osurf protonation in the OER potential range. By including the coverage effect and utilizing the implicit solvent model, we finally show that lattice oxygen mechanism is more feasible than the conventional mechanism for OER on LaNiO3.

11.
J Am Chem Soc ; 139(25): 8758-8765, 2017 06 28.
Artigo em Inglês | MEDLINE | ID: mdl-28560877

RESUMO

Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

12.
Phys Chem Chem Phys ; 19(5): 3575-3581, 2017 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-28094377

RESUMO

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model to aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. This model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.

13.
Nat Mater ; 16(2): 225-229, 2017 02.
Artigo em Inglês | MEDLINE | ID: mdl-27723737

RESUMO

While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.

14.
ChemSusChem ; 9(4): 358-63, 2016 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-26663854

RESUMO

The electrochemical reduction (electroreduction) of CO2 to formic acid (HCOOH) and its competing reactions, that is, the electroreduction of CO2 to CO and the hydrogen evolution reaction (HER), on twenty-seven different metal surfaces have been investigated using density functional theory (DFT) calculations. Owing to a strong linear correlation between the free energies of COOH* and H*, it seems highly unlikely that the electroreduction of CO2 to HCOOH via the COOH* intermediate occurs without a large fraction of the current going to HER. On the other hand, the selective electroreduction of CO2 to HCOOH seems plausible if the reaction occurs via the HCOO* intermediate, as there is little correlation between the free energies of HCOO* and H*. Lead and silver surfaces are found to be the most promising monometallic catalysts showing high faradaic efficiencies for the electroreduction of CO2 to HCOOH with small overpotentials. Our methodology is widely applicable, not only to metal surfaces, but also to other classes of materials enabling the computational search for electrocatalysts for CO2 reduction to HCOOH.


Assuntos
Dióxido de Carbono/química , Técnicas Eletroquímicas/métodos , Formiatos/química , Modelos Teóricos , Metais/química
15.
Chem Commun (Camb) ; 51(13): 2621-4, 2015 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-25571859

RESUMO

During A-H (A = C, N, O) bond cleavage on O* or OH* pre-covered (111) surfaces, the oxygen species play the role of modifying the reaction energy by changing the species involved in the initial and final states of the reaction.

16.
J Phys Chem Lett ; 6(18): 3670-4, 2015 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-26722740

RESUMO

In this Letter, we examine bond activation induced by nonmetal surface promoters in the context of dehydrogenation reactions. We use C-H bond activation in methane dehydrogenation on transition metals as an example to understand the origin of the promoting or poisoning effect of nonmetals. The electronic structure of the surface and the bond order of the promoter are found to establish all trends in bond activation. On the basis of these results, we develop a predictive model that successfully describes the energetics of C-H, O-H, and N-H bond activation across a range of reactions. For a given reaction step, a single data point determines whether a nonmetal will promote bond activation or poison the surface and by how much. We show how our model leads to general insights that can be directly used to predict bond activation energetics on transition metal sulfides and oxides, which can be perceived as promoted surfaces. These results can then be directly used in studies on full catalytic pathways.

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