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1.
ACS Nano ; 2020 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-32672935

RESUMO

We probe the origin of photoluminescence of an atomically precise noble metal cluster, Ag24Au1(DMBT)18, (DMBT = 2,4-dimethylbenzenethiolate) and the origin of chirality in its chirally functionalized derivatives, Ag24Au1(R/S-BINAS)x(DMBT)18-2x, with x = 1-7 (R/S-BINAS = R/S-1,1'-[binaphthalene]-2,2'-dithiol), using chiroptical spectroscopic measurements and density functional theory (DFT) calculations. Combination of chiroptical and luminescence spectroscopies to understand the nature of electronic transitions has not been applied to such molecule-like metal clusters. In order to impart chirality to the achiral Ag24Au1(DMBT)18 cluster, the chiral ligand, R/S-BINAS, was incorporated into it. A series of clusters, Ag24Au1(R/S-BINAS)x(DMBT)18-2x, with x = 1-7 were synthesized. We demonstrate that the low energy electronic transitions undergo an unexpected achiral to chiral and back to achiral transition from pure Ag24Au1(DMBT)18 to Ag24Au1(R/S-BINAS)x(DMBT)18-2x, by increasing the number of BINAS ligands. The UV/Vis, luminescence, circular dichroism and circularly polarized luminescence spectroscopic measurements, in conjunction with DFT calculations suggest that the photoluminescence in Ag24Au1(DMBT)18 and its chirally functionalized derivatives is originated from the transitions involving the whole Ag24Au1S18 framework, not merely from the icosahedral Ag12Au1 core. These results suggest that the chiroptical signatures and photoluminescence in these cluster systems cannot be solely attributed to any one of the structural components, i.e., the metal core or the protecting metal-ligand oligomeric units, but rather to their interaction, and that the ligand shell plays a crucial role. Our work demonstrates that chiroptical spectroscopic techniques such as circular dichroism and circularly polarized luminescence represent useful tools to understand the nature of electronic transitions in ligand protected metal clusters, and that this approach can be utilized for gaining deeper insights into the structure-property relationships of the electronic transitions of such molecule-like clusters.

2.
J Chem Phys ; 152(18): 184104, 2020 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-32414253

RESUMO

A hybrid approach able to perform Time Dependent Density Functional Theory (TDDFT) simulations with the same accuracy as that of hybrid exchange-correlation (xc-) functionals but at a fraction of the computational cost is developed, implemented, and validated. The scheme, which we name Hybrid Diagonal Approximation (HDA), consists in employing in the response function a hybrid xc-functional (containing a fraction of the non-local Hartree-Fock exchange) only for the diagonal elements of the omega matrix, while the adiabatic local density approximation is employed for the off-diagonal terms. HDA is especially (but not exclusively) advantageous when using Slater type orbital basis sets and allows one to employ them in a uniquely efficient way, as we demonstrate here by implementing HDA in a local version of the Amsterdam Density Functional code. The new protocol is tested on NH3, C6H6, and the [Au25(SCH3)18]- cluster as prototypical cases ranging from small molecules to ligand-protected metal clusters, finding excellent agreement with respect to both full kernel TDDFT simulations and experimental data. Additionally, a specific comparison test between full kernel and HDA is considered at the Casida level on seven other molecular species, which further confirm the accuracy of the approach for all investigated systems. For the [Au25(SCH3)18]- cluster, a speedup by a factor of seven is obtained with respect to the full kernel. The HDA, therefore, promises to provide a quantitative description of the optical properties of medium-sized systems (nanoclusters) at an affordable cost, thanks to its computational efficiency, especially in combination with a complex polarization algorithm version of TDDFT.

3.
J Am Chem Soc ; 142(18): 8223-8232, 2020 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-32271551

RESUMO

The Haber-Bosch (HB) process combining nitrogen (N2) and hydrogen (H2) into ammonia (NH3) gas plays an essential role in the synthesis of fertilizers for food production and many other commodities. However, HB requires enormous energy resources (2% of world energy production), and the high pressures and temperatures make NH3 production facilities very expensive. Recent advances in improving HB catalysts have been incremental and slow. To accelerate the development of improved HB catalysts, we developed a hierarchical high-throughput catalyst screening (HHTCS) approach based on the recently developed complete reaction mechanism to identify non-transition-metal (NTM) elements from a total set of 18 candidates that can significantly improve the efficiency of the most active Fe surface, Fe-bcc(111), through surface and subsurface doping. Surprisingly, we found a very promising subsurface dopant, Si, that had not been identified or suggested previously, showing the importance of the subsurface Fe atoms in N2 reduction reactions. Then we derived the full reaction path of the HB process for the Si doped Fe-bcc(111) from QM simulations, which we combined with kinetic Monte Carlo (kMC) simulations to predict a ∼13-fold increase in turnover frequency (TOF) under typical extreme HB conditions (200 atm reactant pressure and 500 °C) and a ∼43-fold increase in TOF under ideal HB conditions (20 atm reactant pressure and 400 °C) for the Si-doped Fe catalyst, in comparison to pure Fe catalyst. Importantly, the Si-doped Fe catalyst can achieve the same TOF of pure Fe at 200 atm/500 °C under much milder conditions, e.g. at a much decreased reactant pressure of 20 atm at 500 °C, or alternatively at temperature and reactant pressure decreased to 400 °C and 60 atm, respectively. Production plants using the new catalysts that operate under such milder conditions could be much less expensive, allowing production at local sites needing fertilizer.

4.
Phys Chem Chem Phys ; 21(22): 11510-11536, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-31114821

RESUMO

Oxide materials at the two-dimensional limit, in particular in the form of ultrathin films of oxides (UTOx) grown on metal surfaces, represent promising materials in view of both fundamental science and technological applications. While the former aspect is widely recognized, these systems have not yet realized their full potential in terms of the latter (technological) aspect. In the present perspective, we review the field and its basic underlying concepts, and at the same time we provide an overview of the most promising future directions with a focus on their potential toward and relationships with real-world exploitation.

5.
Phys Chem Chem Phys ; 21(21): 11444-11454, 2019 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-31112166

RESUMO

To provide guidelines to accelerate the Haber-Bosch (HB) process for synthesis of ammonia from hydrogen and nitrogen, we used Quantum Mechanics (QM) to determine the reaction mechanism and free energy reaction barriers under experimental reaction conditions (400 °C and 20 atm) for all 10 important surface reactions on the Fe(211) reconstructed (Fe(211)R) surface. These conditions were then used in full kMC modeling for 30 minutes to attain steady state. We find that the stable surface under Haber-Bosch conditions is the missing row 2 × 1 reconstructed surface (211)R and that the Turn Over Frequency (TOF) is 18.7 s-1 per 2 × 2 surface site for 1.5 Torr NH3 pressure, but changes to 3.5 s-1 for 1 atm, values close (within 6%) to the ones on Fe(111). The experimental ratio between (211) and (111) rates at low (undisclosed) NH3 pressure was reported to be 0.75. The excellent agreement with experiment on two very different surfaces and reaction mechanisms is a testament of the accuracy of QM modeling. In addition, our kinetic analysis indicates that Fe(211)R is more active than Fe(111) at high pressure, close to HB industrial conditions, and that (211)R is more abundant than (111) via a steady-state Wulff construction under HB conditions. Thus, at variance with common thinking, we advocate the Fe(211)R surface as the catalytically active phase of pure iron ammonia synthesis catalyst under HB industrial conditions.

6.
Proc Natl Acad Sci U S A ; 116(16): 7718-7722, 2019 04 16.
Artigo em Inglês | MEDLINE | ID: mdl-30867281

RESUMO

Electrocatalysis provides a powerful means to selectively transform molecules, but a serious impediment in making rapid progress is the lack of a molecular-based understanding of the reactive mechanisms or intermediates at the electrode-electrolyte interface (EEI). Recent experimental techniques have been developed for operando identification of reaction intermediates using surface infrared (IR) and Raman spectroscopy. However, large noises in the experimental spectrum pose great challenges in resolving the atomistic structures of reactive intermediates. To provide an interpretation of these experimental studies and target for additional studies, we report the results from quantum mechanics molecular dynamics (QM-MD) with explicit consideration of solvent, electrode-electrolyte interface, and applied potential at 298 K, which conceptually resemble the operando experimental condition, leading to a prototype of operando QM-MD (o-QM-MD). With o-QM-MD, we characterize 22 possible reactive intermediates in carbon dioxide reduction reactions ([Formula: see text]RRs). Furthermore, we report the vibrational density of states (v-DoSs) of these intermediates from two-phase thermodynamic (2PT) analysis. Accordingly, we identify important intermediates such as chemisorbed [Formula: see text] ([Formula: see text]), *HOC-COH, *C-CH, and *C-COH in our o-QM-MD likely to explain the experimental spectrum. Indeed, we assign the experimental peak at 1,191 cm-1 to the mode of C-O stretch in *HOC-COH predicted at 1,189 cm-1 and the experimental peak at 1,584 cm-1 to the mode of C-C stretch in *C-COD predicted at 1,581 cm-1 Interestingly, we find that surface ketene (*C=C=O), arising from *HOC-COH dehydration, also shows signals at around 1,584 cm-1, which indicates a nonelectrochemical pathway of hydrocarbon formation at low overpotential and high pH conditions.

7.
Phys Chem Chem Phys ; 21(7): 3585-3596, 2019 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-30255885

RESUMO

TDDFT simulations of the absorption and CD spectra of a Pd2Au36(SC2H4Ph)24 monolayer-protected cluster (MPC) are carried out with the aim of investigating the effects of doping, conformational degrees of freedom of the thiolates' end-groups, and charge states on the optical and dichroic response of a prototypical MPC species. Clear signatures of Pd doping in both absorption and CD spectra are found to be a consequence of the participation of Pd (4d) states in the ligand-based d-band and on the unoccupied MOs of lower energy. Exploration of conformational space points to a much greater sensitivity of optical rotation to the conformation of the end-groups of the organic monolayer compared to absorption. Finally, the effect of charge is mainly seen as a decreased dependence of the dichroic response on conformation. The agreement between the TDDFT predictions and the available experimental data is good, and enables an assignment of absorption and CD bands to specific classes of one-particle excitations.

8.
J Am Chem Soc ; 140(50): 17702-17710, 2018 12 19.
Artigo em Inglês | MEDLINE | ID: mdl-30479122

RESUMO

We propose and test a hierarchical high-throughput screening (HHTS) approach to catalyst design for complex catalytic reaction systems that is based on quantum mechanics (QM) derived full reaction networks with QM rate constants but simplified to examine only the reaction steps likely to be rate determining. We illustrate this approach by applying it to determine the optimum dopants (our of 35 candidates) to improve the turnover frequency (TOF) for the Fe-based Haber-Bosch ammonia synthesis process. We start from the QM-based free-energy reaction network for this reaction over Fe(111), which contains the 26 most important surface configurations and 17 transition states at operating conditions of temperature and pressure, from which we select the key reaction steps that might become rate determining for the alloy. These are arranged hierarchically by decreasing free-energy reaction barriers. We then extract from the full reaction network, a reduced set of reaction rates required to quickly predict the effect of the catalyst changes on each barrier. This allows us to test new candidates with only 1% of the effort for a full calculation. Thus, we were able to quickly screen 34 candidate dopants to select a small subset (Rh, Pt, Pd, Cu) that satisfy all criteria, including stability. Then from these four candidates expected to increase the TOF for NH3 production, we selected the best candidate (Rh) for a more complete free-energy and kinetic analysis (10 times the effort for HHTS but still 10% of the effort for a complete analysis of the full reaction network). We predict that Rh doping of Fe will increase the TOF for NH3 synthesis by a factor of ∼3.3 times compared to Fe(111), in excellent agreement with our HHTS predictions, validating this approach.

9.
Nanoscale ; 10(37): 17730-17737, 2018 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-30209457

RESUMO

We propose and investigate computationally Ag-Au subnanometer clusters as catalysts for the hydrogen evolution reaction (HER). Focusing on Ag12Au, we conduct a complete first-principles study of the HER process on this Au@Ag ultrananocatalyst. After determining the hydrogen-saturated resting state under standard conditions as Ag12AuH11, HER reaction energies and barriers are predicted also including solvent effects using both implicit and explicit models. We find that Ag12Au is a good candidate as a HER catalyst, with good stability and an overall reaction energy barrier of 0.89 eV as an upper bound. We also draw indications for the design of HER subnanometer catalysts.

10.
Front Chem ; 6: 330, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30131953

RESUMO

The nature of the ligands dictates the composition, molecular formulae, atomic structure and the physical properties of thiolate protected gold nanomolecules, Aun(SR)m. In this review, we describe the ligand effect for three classes of thiols namely, aliphatic, AL or aliphatic-like, aromatic, AR, or bulky, BU thiol ligands. The ligand effect is demonstrated using three experimental setups namely: (1) The nanomolecule series obtained by direct synthesis using AL, AR, and BU ligands; (2) Molecular conversion and interconversion between Au38(S-AL)24, Au36(S-AR)24, and Au30(S-BU)18 nanomolecules; and (3) Synthesis of Au38, Au36, and Au30 nanomolecules from one precursor Aun(S-glutathione)m upon reacting with AL, AR, and BU ligands. These nanomolecules possess unique geometric core structure, metal-ligand staple interface, optical and electrochemical properties. The results unequivocally demonstrate that the ligand structure determines the nanomolecules' atomic structure, metal-ligand interface and properties. The direct synthesis approach reveals that AL, AR, and BU ligands form nanomolecules with unique atomic structure and composition. Similarly, the nature of the ligand plays a pivotal role and has a significant impact on the passivated systems such as metal nanoparticles, quantum dots, magnetic nanoparticles and self-assembled monolayers (SAMs). Computational analysis demonstrates and predicts the thermodynamic stability of gold nanomolecules and the importance of ligand-ligand interactions that clearly stands out as a determining factor, especially for species with AL ligands such as Au38(S-AL)24.

11.
J Chem Theory Comput ; 14(7): 3703-3714, 2018 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-29897750

RESUMO

We introduce individual component maps of rotatory strength (ICM-RS) and rotatory strength density (RSD) plots as analysis tools of chiro-optical linear response spectra deriving from time-dependent density functional theory (TDDFT) simulations. ICM-RS and RSD allow one to visualize the origin of chiro-optical response in momentum or real space, including signed contributions and therefore highlighting cancellation terms that are ubiquitous in chirality phenomena, and should be especially useful in analyzing the spectra of complex systems. As test cases, we use ICM-RS and RSD to analyze circular dichroism spectra of selected (Ag-Au)30(SR)18 monolayer-protected metal nanoclusters, showing the potential of the proposed tools to derive insight and understanding, and eventually rational design, in chiro-optical studies of complex systems.

12.
Phys Chem Chem Phys ; 20(19): 13255-13262, 2018 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-29737991

RESUMO

Here, we report the synthesis of selenophenol (HSePh) protected Au36(SePh)24 nanomolecules via a ligand-exchange reaction of 4-tert-butylbenzenethiol (HSPh-tBu) protected Au36(SPh-tBu)24 with selenophenol, and its spectroscopic and theoretical analysis. Matrix assisted laser desorption ionization (MALDI) mass spectrometry, electrospray ionization (ESI) mass spectrometry and optical characterization confirm that the composition of the as synthesized product is predominantly Au36(SePh)24 nanomolecules. Size exclusion chromatography (SEC) was employed to isolate the Au36(SePh)24 and temperature dependent optical absorption studies and theoretical analysis were performed. Theoretically, an Independent Component Maps of Oscillator Strength (ICM-OS) analysis of simulated spectra shows that the enhancement in absorption intensity in Au36(SePh)24 with respect to Au36(SPh)24 can be ascribed to the absence of interference and/or increased long-range coupling between interband metal core and ligand excitations. This work demonstrates and helps to understand the effect of Au-Se bridging on the properties of gold nanomolecules.

13.
J Am Chem Soc ; 140(20): 6288-6297, 2018 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-29701965

RESUMO

The Haber-Bosch industrial process for synthesis of ammonia (NH3) from hydrogen and nitrogen produces the millions of tons of ammonia gas annually needed to produce nitrates for fertilizers required to feed the earth's growing populations. This process has been optimized extensively, but it still uses enormous amounts of energy (2% of the world's supply), making it essential to dramatically improve its efficiency. To provide guidelines to accelerate this improvement, we used quantum mechanics to predict reaction mechanisms and kinetics for NH3 synthesis on Fe(111)-the best Fe single crystal surface for NH3 synthesis. We predicted the free energies of all reaction barriers for all steps in the mechanism and built these results into a kinetic Monte Carlo model for predicting steady state catalytic rates to compare with single-crystal experiments at 673 K and 20 atm. We find excellent agreement with a predicted turnover frequency (TOF) of 17.7 s-1 per 2 × 2 site (5.3 × 10-9 mol/cm2/sec) compared to TOF = 10 s-1 per site from experiment.

14.
J Chem Phys ; 148(11): 110901, 2018 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-29566496

RESUMO

Size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization, and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition, cluster-support interactions, and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modeling based on density functional theory sampling of local minima and energy barriers or ab initio molecular dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Finally, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.

15.
J Phys Chem Lett ; 9(6): 1295-1300, 2018 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-29493241

RESUMO

We report a detailed study on the optical properties of Au279(SR)84 using steady-state and transient absorption measurements to probe its metallic nature, time-dependent density functional theory (TDDFT) studies to correlate the optical spectra, and density of states (DOS) to reveal the factors governing the origin of the collective surface plasmon resonance (SPR) oscillation. Au279 is the smallest identified gold nanocrystal to exhibit SPR. Its optical absorption exhibits SPR at 510 nm. Power-dependent bleach recovery kinetics of Au279 suggests that electron dynamics dominates its relaxation and it can support plasmon oscillations. Interestingly, TDDFT and DOS studies with different tail group residues (-CH3 and -Ph) revealed the important role played by the tail groups of ligands in collective oscillation. Also, steady-state and time-resolved absorption for Au36, Au44, and Au133 were studied to reveal the molecule-to-metal evolution of aromatic AuNMs. The optical gap and transient decay lifetimes decrease as the size increases.

16.
Chem Sci ; 9(47): 8796-8805, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30647884

RESUMO

For two decades, Au144(SR)60 has been one of the most studied and used thiolate (SR) protected gold nanoclusters. In many ways, however, it proved to be a challenging and elusive case, also because of the difficulties in solving its structure by single-crystal X-ray crystallography. We used very short thiols and could prepare Au144(SC2H5)60 and Au144(SC3H7)60 in a very pure form, which was confirmed by UV-vis absorption spectroscopy and very regular electrochemistry patterns. Inductively coupled plasma and electrospray ionization mass spectrometries gave definite proof of the Au144(SR)60 stoichiometry. High-resolution 1D and 2D NMR spectroscopy in the solution phase provided the result of assessing the presence of 12 ligand types in exactly the same amount (5-fold equivalence). Equally important, we found that the two protons belonging to each methylene group along the thiolate chain are diastereotopic. For the α-CH2 protons, the diastereotopic effect can be indeed gigantic, as it reaches chemical-shift differences of 2.9 ppm. DFT calculations provided insights into the relationship between structure and NMR results. In particular, the 12 ligand types and corresponding diastereotopic effects may be explained by considering the presence of C-H···S hydrogen bonds. These results thus provide fundamental insights into the structure of the thiolate layer capping this long-studied gold nanocluster.

17.
Angew Chem Int Ed Engl ; 57(5): 1209-1213, 2018 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-29239093

RESUMO

A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO→CO2 reaction (COox) is presented. Ag9 Pt2 and Ag9 Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. In situ GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O2 , and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.

19.
J Chem Phys ; 147(7): 074301, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28830181

RESUMO

Ligand-protected Au clusters are non-bleaching fluorescence markers in bio- and medical applications. Here we show that their fluorescence can be an intrinsic property of the Au cluster itself. We find a very intense and sharp fluorescence peak located at λ=739.2 nm (1.68 eV) for Au20 clusters in a Ne matrix held at 6 K. The fluorescence reflects the Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO-LUMO) diabatic bandgap of the cluster. Au20 shows a very rich absorption fine structure reminiscent of well defined molecule-like quantum levels. These levels are resolved since Au20 has only one stable isomer (tetrahedral); therefore our sample is mono-disperse in cluster size and conformation. Density-functional theory (DFT) and time-dependent DFT calculations clarify the nature of optical absorption and predict both main absorption peaks and intrinsic fluorescence in fair agreement with experiment.

20.
Sci Rep ; 7(1): 5109, 2017 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-28698652

RESUMO

The performance of devices and systems based on two-dimensional material systems depends critically on the quality of the contacts between 2D material and metal. A low contact resistance is an imperative requirement to consider graphene as a candidate material for electronic and optoelectronic devices. Unfortunately, measurements of contact resistance in the literature do not provide a consistent picture, due to limitations of current graphene technology, and to incomplete understanding of influencing factors. Here we show that the contact resistance is intrinsically dependent on graphene sheet resistance and on the chemistry of the graphene-metal interface. We present a physical model of the contacts based on ab-initio simulations and extensive experiments carried out on a large variety of samples with different graphene-metal contacts. Our model explains the spread in experimental results as due to uncontrolled graphene doping and suggests ways to engineer contact resistance. We also predict an achievable contact resistance of 30 Ω·µm for nickel electrodes, extremely promising for applications.

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