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1.
Nat Nanotechnol ; 2020 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-33318640

RESUMO

Ammonia, one of the most important synthetic feedstocks, is mainly produced by the Haber-Bosch process at 400-500 °C and above 100 bar. The process cannot be performed under ambient conditions for kinetic reasons. Here, we demonstrate that ammonia can be synthesized at 45 °C and 1 bar via a mechanochemical method using an iron-based catalyst. With this process the ammonia final concentration reached 82.5 vol%, which is higher than state-of-the-art ammonia synthesis under high temperature and pressure (25 vol%, 450 °C, 200 bar). The mechanochemically induced high defect density and violent impact on the iron catalyst were responsible for the mild synthesis conditions.

2.
J Phys Chem Lett ; 11(23): 10029-10036, 2020 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-33179928

RESUMO

It has been well-established that unfavorable scaling relationships between *OOH, *OH, and *O are responsible for the high overpotentials associated with oxygen electrochemistry. A number of strategies have been proposed for breaking these linear constraints for traditional electrocatalysts (e.g., metals, alloys, metal-doped carbons); such approaches have not yet been validated experimentally for heterogeneous catalysts. Development of a new class of catalysts capable of circumventing such scaling relations remains an ongoing challenge in the field. In this work, we use density functional theory (DFT) calculations to demonstrate that bimetallic porphyrin-based MOFs (PMOFs) are an ideal materials platform for rationally designing the 3-D active site environments for oxygen reduction reaction (ORR). Specifically, we show that the *OOH binding energy and the theoretical limiting potential can be optimized by appropriately tuning the transition metal active site, the oxophilic spectator, and the MOF topology. Our calculations predict theoretical limiting potentials as high as 1.07 V for Fe/Cr-PMOF-Al, which exceeds the Pt/C benchmark for 4e ORR. More broadly, by highlighting their unique characteristics, this work aims to establish bimetallic porphyrin-based MOFs as a viable materials platform for future experimental and theoretical ORR studies.

3.
Adv Mater ; 32(37): e2003020, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32743836

RESUMO

Forming pits on molybdenum disulfide (MoS2 ) monolayers is desirable for (opto)electrical, catalytic, and biological applications. Thermal oxidation is a potentially scalable method to generate pits on monolayer MoS2 , and pits are assumed to preferentially form around undercoordinated sites, such as sulfur vacancies. However, studies on thermal oxidation of MoS2 monolayers have not considered the effect of adventitious carbon (C) that is ubiquitous and interacts with oxygen at elevated temperatures. Herein, the effect of adventitious C on the pit formation on MoS2 monolayers during thermal oxidation is studied. The in situ environmental transmission electron microscopy measurements herein show that pit formation is preferentially initiated at the interface between adventitious C nanoparticles and MoS2 , rather than only sulfur vacancies. Density functional theory (DFT) calculations reveal that the C/MoS2 interface favors the sequential adsorption of oxygen atoms with facile kinetics. These results illustrate the important role of adventitious C on pit formation on monolayer MoS2 .

4.
J Am Chem Soc ; 142(36): 15386-15395, 2020 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-32786758

RESUMO

The oxygen reduction reaction (ORR) is central in carbon-neutral energy devices. While platinum group materials have shown high activities for ORR, their practical uses are hampered by concerns over deactivation, slow kinetics, exorbitant cost, and scarce nature reserve. The low cost yet high tunability of metal-organic frameworks (MOFs) provide a unique platform for tailoring their characteristic properties as new electrocatalysts. Herein, we report a new concept of design and present stable Zr-chain-based MOFs as efficient electrocatalysts for ORR. The strategy is based on using Zr-chains to promote high chemical and redox stability and, more importantly, tailor the immobilization and packing of redox active-sites at a density that is ideal to improve the reaction kinetics. The obtained new electrocatalyst, PCN-226, thereby shows high ORR activity. We further demonstrate PCN-226 as a promising electrode material for practical applications in rechargeable Zn-air batteries, with a high peak power density of 133 mW cm-2. Being one of the very few electrocatalytic MOFs for ORR, this work provides a new concept by designing chain-based structures to enrich the diversity of efficient electrocatalysts and MOFs.

5.
Nat Commun ; 11(1): 2178, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32358548

RESUMO

Electrochemical synthesis of H2O2 through a selective two-electron (2e-) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H2O2 production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pdδ+) and oxygen-functionalized carbon can promote 2e- ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pdδ+ clusters (Pd3δ+ and Pd4δ+) onto mildly oxidized carbon nanotubes (Pdδ+-OCNT) shows nearly 100% selectivity toward H2O2 and a positive shift of ORR onset potential by ~320 mV compared with the OCNT substrate. A high mass activity (1.946 A mg-1 at 0.45 V) of Pdδ+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e- ORR.

6.
Nat Commun ; 11(1): 2209, 2020 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-32371867

RESUMO

The one-step electrochemical synthesis of H2O2 is an on-site method that reduces dependence on the energy-intensive anthraquinone process. Oxidized carbon materials have proven to be promising catalysts due to their low cost and facile synthetic procedures. However, the nature of the active sites is still controversial, and direct experimental evidence is presently lacking. Here, we activate a carbon material with dangling edge sites and then decorate them with targeted functional groups. We show that quinone-enriched samples exhibit high selectivity and activity with a H2O2 yield ratio of up to 97.8 % at 0.75 V vs. RHE. Using density functional theory calculations, we identify the activity trends of different possible quinone functional groups in the edge and basal plane of the carbon nanostructure and determine the most active motif. Our findings provide guidelines for designing carbon-based catalysts, which have simultaneous high selectivity and activity for H2O2 synthesis.

7.
Nat Commun ; 10(1): 3997, 2019 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-31488826

RESUMO

Shifting electrochemical oxygen reduction towards 2e- pathway to hydrogen peroxide (H2O2), instead of the traditional 4e- to water, becomes increasingly important as a green method for H2O2 generation. Here, through a flexible control of oxygen reduction pathways on different transition metal single atom coordination in carbon nanotube, we discovered Fe-C-O as an efficient H2O2 catalyst, with an unprecedented onset of 0.822 V versus reversible hydrogen electrode in 0.1 M KOH to deliver 0.1 mA cm-2 H2O2 current, and a high H2O2 selectivity of above 95% in both alkaline and neutral pH. A wide range tuning of 2e-/4e- ORR pathways was achieved via different metal centers or neighboring metalloid coordination. Density functional theory calculations indicate that the Fe-C-O motifs, in a sharp contrast to the well-known Fe-C-N for 4e-, are responsible for the H2O2 pathway. This iron single atom catalyst demonstrated an effective water disinfection as a representative application.

8.
ACS Appl Mater Interfaces ; 11(30): 26863-26871, 2019 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-31310093

RESUMO

With promising activity and stability for the oxygen reduction reaction (ORR), transition metal nitrides are an interesting class of non-platinum group catalysts for polymer electrolyte membrane fuel cells. Here, we report an active thin-film nickel nitride catalyst synthesized through a reactive sputtering method. In rotating disk electrode testing in a 0.1 M HClO4 electrolyte, the crystalline nickel nitride film achieved high activity and selectivity to four-electron ORR. It also exhibited good stability during 10 and 40 h chronoamperometry measurements in acid and alkaline electrolyte, respectively. A combined experiment-theory approach, with detailed ex situ materials characterization and density functional theory calculations, provides insight into the structure of the catalyst and its surface during catalysis. Design strategies for activity and stability improvement through alloying and nanostructuring are discussed.

9.
ACS Appl Mater Interfaces ; 11(2): 2006-2013, 2019 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-30582334

RESUMO

Developing cost-effective oxygen electrocatalysts with high activity and stability is key to their commercialization. However, economical earth-abundant catalysts based on first-row transition-metal oxides suffer from low electrochemical stability, which is difficult to improve without compromising their activity. Here, using density functional theory calculations, we demonstrate that noble-metal supports lead to bifunctional enhancement of both the stability and the oxygen reduction reaction (ORR) activity of metal (oxy-hydro) oxide nanoislands. We observe a significant stabilization of supported nanoislands beyond the intrinsic stability limits of bulk phases, which originates from a favorable lattice mismatch and reductive charge transfer from oxophilic supports. We discover that interfacial active sites (located between the nanoisland and the support) reinforce the binding strength of reaction intermediates, hence boosting ORR activity. Considering that both stability and activity lead to discovery of CoOOH|Pt, NiOOH|Ag, and FeO2|Ag as viable systems for alkaline ORR, we then use a multivariant linear regression method to identify elementary descriptors for efficient screening of promising cost-effective nanoisland|support catalysts.

10.
J Am Chem Soc ; 140(25): 7851-7859, 2018 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-29874062

RESUMO

Heteroatom-doped carbons have drawn increasing research interest as catalysts for various electrochemical reactions due to their unique electronic and surface structures. In particular, co-doping of carbon with boron and nitrogen has been shown to provide significant catalytic activity for oxygen reduction reaction (ORR). However, limited experimental work has been done to systematically study these materials, and much remains to be understood about the nature of the active site(s), particularly with regards to the factors underlying the activity enhancements of these boron-carbon-nitrogen (BCN) materials. Herein, we prepare several BCN materials experimentally with a facile and controlled synthesis method, and systematically study their electrochemical performance. We demonstrate the existence of h-BN domains embedded in the graphitic structures of these materials using X-ray spectroscopy. These synthesized structures yield higher activity and selectivity toward the 2e- ORR to H2O2 than structures with individual B or N doping. We further employ density functional theory calculations to understand the role of a variety of h-BN domains within the carbon lattice for the ORR and find that the interface between h-BN domains and graphene exhibits unique catalytic behavior that can preferentially drive the production of H2O2. To the best of our knowledge, this is the first example of h-BN domains in carbon identified as a novel system for the electrochemical production of H2O2.

11.
Angew Chem Int Ed Engl ; 57(30): 9392-9396, 2018 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-29889350

RESUMO

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel-iron layered double hydroxides (NiFe-LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe-O-Fe moieties. These Fe2+ -containing NiFe-LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm-2 , which is among the best OER catalytic performance to date. In-situ X-ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe-O-Fe motifs could stabilize high-valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.

12.
Inorg Chem ; 57(12): 7222-7238, 2018 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-29863849

RESUMO

We investigate the (surface) bonding of a class of industrially and biologically important molecules in which the chemically active orbital is a 2 p electron lone pair located on an N or O atom bound via single bonds to H or alkyl groups. This class includes water, ammonia, alcohols, ethers, and amines. Using extensive density functional theory (DFT) calculations, we discover scaling relations (correlations) among molecular binding energies of different members of this class: the bonding energetics of a single member can be used as a descriptor for other members. We investigate the bonding mechanism for a representative (H2O) and find the most important physical surface properties that dictate the strength and nature of the bonding through a combination of covalent and noncovalent electrostatic effects. We describe the importance of surface intrinsic electrostatic, geometric, and mechanical properties in determining the extent of the lone-pair-surface interactions. We study systems including ionic materials in which the surface positive and negative centers create strong local surface electric fields, which polarize the dangling lone pair and lead to a strong "electrostatically driven bond". We emphasize the importance of noncovalent electrostatic effects and discuss why a fully covalent picture, common in the current first-principles literature on surface bonding of these molecules, is not adequate to correctly describe the bonding mechanism and energy trends. By pointing out a completely different mechanism (charge transfer) as the major factor for binding N- and O-containing unsaturated (radical) adsorbates, we explain why their binding energies can be tuned independently from those of the aforementioned species, having potential implications in scaling-driven catalyst discovery.

13.
Chem Rev ; 118(5): 2302-2312, 2018 03 14.
Artigo em Inglês | MEDLINE | ID: mdl-29405702

RESUMO

Despite the dedicated search for novel catalysts for fuel cell applications, the intrinsic oxygen reduction reaction (ORR) activity of materials has not improved significantly over the past decade. Here, we review the role of theory in understanding the ORR mechanism and highlight the descriptor-based approaches that have been used to identify catalysts with increased activity. Specifically, by showing that the performance of the commonly studied materials (e.g., metals, alloys, carbons, etc.) is limited by unfavorable scaling relationships (for binding energies of reaction intermediates), we present a number of alternative strategies that may lead to the design and discovery of more promising materials for ORR.

14.
Nat Commun ; 8(1): 701, 2017 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-28951571

RESUMO

Electrochemical production of hydrogen peroxide (H2O2) from water oxidation could provide a very attractive route to locally produce a chemically valuable product from an abundant resource. Herein using density functional theory calculations, we predict trends in activity for water oxidation towards H2O2 evolution on four different metal oxides, i.e., WO3, SnO2, TiO2 and BiVO4. The density functional theory predicted trend for H2O2 evolution is further confirmed by our experimental measurements. Moreover, we identify that BiVO4 has the best H2O2 generation amount of those oxides and can achieve a Faraday efficiency of about 98% for H2O2 production.Producing hydrogen peroxide via electrochemical oxidation of water is an attractive route to this valuable product. Here the authors theoretically and experimentally investigate hydrogen peroxide production activity trends for a range of metal oxides and identify the optimal bias ranges for high Faraday efficiencies.

15.
J Phys Chem Lett ; 8(6): 1157-1160, 2017 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-28231706

RESUMO

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H2O2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O2 evolution. We develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H2O2, and O2.

16.
ACS Cent Sci ; 3(12): 1286-1293, 2017 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-29296669

RESUMO

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton-electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from CO to be a critical step in C1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. This work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.

17.
Phys Chem Chem Phys ; 16(20): 9572-9, 2014 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-24728561

RESUMO

Sulphur dioxide (SO2), a known industrial pollutant and pulmonary irritant, is emitted to the atmosphere in excess of 120 Mt per annum. Great strides have been taken to reduce SO2 emissions, but with the growth of specifically China, and to a lesser extent India, it is on the rise again. The electrolysis of aqueous solutions of dissolved SO2 holds huge environmental potential in that SO2 is converted to sulphuric acid (H2SO4) and at the same time hydrogen gas is produced. A further benefit or incentive is that a sulphur depolarised electrolyser (SDE) operates at an applied potential that is about one volt lower than that of a regular water electrolyser. In taking this technology forward the greatest improvement to be made is in developing a suitable electrocatalyst, which is also the 'lowest hanging fruit' in that very limited research and development has been conducted on the electrocatalyst for this process. In this work, density functional theory is employed to model the electro-oxidation of SO2 on single crystal planes of the 4d and 5d transition metals. Two reaction mechanisms are considered, a HSO3 intermediate pathway and a SO3 intermediate pathway. The binding energies of all intermediates are found to scale with the surface reactivity (measured as the adsorption of OH). Irrespective of the pathway water needs to be activated and reduction of SO2 to elemental sulphur must be avoided. This requirement alone calls for an electrode potential of at least 0.7-0.8 V for all the investigated transition metals and thus challenges the proclaimed goal to operate the SDE at 0.6 V. A high chemical barrier is further found to severely limit the oxidation reaction on reactive metals. A much higher catalytic activity can be obtained on precious metals but at the cost of running the reaction at high overpotentials.

18.
Nano Lett ; 14(3): 1603-8, 2014 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-24506229

RESUMO

The direct electrochemical synthesis of hydrogen peroxide is a promising alternative to currently used batch synthesis methods. Its industrial viability is dependent on the effective catalysis of the reduction of oxygen at the cathode. Herein, we study the factors controlling activity and selectivity for H2O2 production on metal surfaces. Using this approach, we discover two new catalysts for the reaction, Ag-Hg and Pd-Hg, with unique electrocatalytic properties both of which exhibit performance that far exceeds the current state-of-the art.

19.
Nat Mater ; 12(12): 1137-43, 2013 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-24240242

RESUMO

Future generations require more efficient and localized processes for energy conversion and chemical synthesis. The continuous on-site production of hydrogen peroxide would provide an attractive alternative to the present state-of-the-art, which is based on the complex anthraquinone process. The electrochemical reduction of oxygen to hydrogen peroxide is a particularly promising means of achieving this aim. However, it would require active, selective and stable materials to catalyse the reaction. Although progress has been made in this respect, further improvements through the development of new electrocatalysts are needed. Using density functional theory calculations, we identify Pt-Hg as a promising candidate. Electrochemical measurements on Pt-Hg nanoparticles show more than an order of magnitude improvement in mass activity, that is, A g(-1) precious metal, for H2O2 production, over the best performing catalysts in the literature.

20.
Phys Chem Chem Phys ; 15(23): 9326-34, 2013 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-23661187

RESUMO

The efficiency of proton exchange membrane fuel cells is limited mainly by the oxygen reduction reaction at the cathode. The large cathodic overpotential is caused by correlations between binding energies of reaction intermediates in the reduction of oxygen to water. This work introduces a novel tandem cathode design where the full oxygen reduction, involving four electron-transfer steps, is divided into formation (equilibrium potential 0.70 V) followed by reduction (equilibrium potential 1.76 V) of hydrogen peroxide. The two part reactions contain only two electron-transfer steps and one reaction intermediate each, and they occur on different catalyst surfaces. As a result they can be optimized independently and the fundamental problem associated with the four-electron catalysis is avoided. A combination of density functional theory calculations and published experimental data is used to identify potentially active and selective materials for both catalysts. Co-porphyrin is recommended for the first step, formation of hydrogen peroxide, and three different metal oxides - SrTiO3(100), CaTiO3(100) and WO3(100) - are suggested for the subsequent reduction step.

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