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1.
ACS Appl Mater Interfaces ; 16(21): 27230-27241, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38752720

ABSTRACT

The reactivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolytes to form lithio-phobic species such as Li2CO3 on their surface when exposed to trace amounts of H2O and CO2 limits the progress of LLZTO-based solid-state batteries. Various treatments, such as annealing LLZTO within a glovebox or acid etching, aim at removing the surface contaminants, but a comprehensive understanding of the evolving LLZTO surface chemistry during and after these treatments is lacking. Here, glovebox-like H2O and CO2 conditions were recreated in a near ambient pressure X-ray photoelectron spectroscopy chamber to analyze the LLZTO surface under realistic conditions. We find that annealing LLZTO at 600 °C in this atmosphere effectively removes the surface contaminants, but a significant level of contamination reappears upon cooling down. In contrast, HCl(aq) acid etching demonstrates superior Li2CO3 removal and stable surface chemistry post treatment. To avoid air exposure during the acid treatment, an anhydrous HCl solution in diethyl ether was used directly within the glovebox. This novel acid etching strategy delivers the lowest lithium/LLZTO interfacial resistance and the highest critical current density.

2.
ACS Catal ; 13(14): 9558-9566, 2023 Jul 21.
Article in English | MEDLINE | ID: mdl-37497376

ABSTRACT

Single-site catalysts (SSCs) have attracted significant research interest due to their high metal atom utilization. Platinum single sites trapped in the defects of carbon substrates (trapped Pt-SSCs) have been proposed as efficient and stable electrocatalysts for the hydrogen evolution reaction (HER). However, the correlation between Pt bonding environment, its evolution during operation, and catalytic activity is still unclear. Here, a trapped Pt-SSC is synthesized by pyrolysis of H2PtCl6 chemisorbed on a polyaniline substrate. In situ heated scanning transmission electron microscopy and temperature-dependent X-ray photoelectron spectroscopy clarify the thermally induced structural evolution of Pt during pyrolysis. The results show that the nitrogen in polyaniline coordinates with Pt ions and atomically disperses them before pyrolysis and traps Pt sites at pyridinic N defects generated during the substrate graphitization. Operando X-ray absorption spectroscopy confirms that the trapped Pt-SSC is stable at the HER working potentials but with inferior electrocatalytic activity compared with metallic Pt nanoparticles. First principle calculations suggest that the inferior activity of trapped Pt-SSCs is due to their unfavorable hydrogen chemisorption energy relative to metallic Pt(111) surfaces. These results further the understanding of the structure-property relationship in trapped Pt-SSCs and motivate a detailed techno-economic analysis to evaluate their commercial applicability.

3.
J Am Chem Soc ; 145(12): 6730-6740, 2023 Mar 29.
Article in English | MEDLINE | ID: mdl-36916242

ABSTRACT

The reactions of H2, CO2, and CO gas mixtures on the surface of Cu at 200 °C, relevant for industrial methanol synthesis, are investigated using a combination of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and atmospheric-pressure near edge X-ray absorption fine structure (AtmP-NEXAFS) spectroscopy bridging pressures from 0.1 mbar to 1 bar. We find that the order of gas dosing can critically affect the catalyst chemical state, with the Cu catalyst maintained in a metallic state when H2 is introduced prior to the addition of CO2. Only on increasing the CO2 partial pressure is CuO formation observed that coexists with metallic Cu. When only CO2 is present, the surface oxidizes to Cu2O and CuO, and the subsequent addition of H2 partially reduces the surface to Cu2O without recovering metallic Cu, consistent with a high kinetic barrier to H2 dissociation on Cu2O. The addition of CO to the gas mixture is found to play a key role in removing adsorbed oxygen that otherwise passivates the Cu surface, making metallic Cu surface sites available for CO2 activation and subsequent conversion to CH3OH. These findings are corroborated by mass spectrometry measurements, which show increased H2O formation when H2 is dosed before rather than after CO2. The importance of maintaining metallic Cu sites during the methanol synthesis reaction is thereby highlighted, with the inclusion of CO in the gas feed helping to achieve this even in the absence of ZnO as the catalyst support.

4.
J Phys Chem C Nanomater Interfaces ; 126(49): 21022-21033, 2022 Dec 15.
Article in English | MEDLINE | ID: mdl-36561200

ABSTRACT

A comprehensive study of bulk molybdenum dichalcogenides is presented with the use of soft and hard X-ray photoelectron (SXPS and HAXPES) spectroscopy combined with hybrid density functional theory (DFT). The main core levels of MoS2, MoSe2, and MoTe2 are explored. Laboratory-based X-ray photoelectron spectroscopy (XPS) is used to determine the ionization potential (IP) values of the MoX2 series as 5.86, 5.40, and 5.00 eV for MoSe2, MoSe2, and MoTe2, respectively, enabling the band alignment of the series to be established. Finally, the valence band measurements are compared with the calculated density of states which shows the role of p-d hybridization in these materials. Down the group, an increase in the p-d hybridization from the sulfide to the telluride is observed, explained by the configuration energy of the chalcogen p orbitals becoming closer to that of the valence Mo 4d orbitals. This pushes the valence band maximum closer to the vacuum level, explaining the decreasing IP down the series. High-resolution SXPS and HAXPES core-level spectra address the shortcomings of the XPS analysis in the literature. Furthermore, the experimentally determined band alignment can be used to inform future device work.

5.
Nat Commun ; 13(1): 6070, 2022 Oct 14.
Article in English | MEDLINE | ID: mdl-36241622

ABSTRACT

The solid electrolyte interphase (SEI) that forms on Li-ion battery anodes is critical to their long-term performance, however observing SEI formation processes at the buried electrode-electrolyte interface is a significant challenge. Here we show that operando soft X-ray absorption spectroscopy in total electron yield mode can resolve the chemical evolution of the SEI during electrochemical formation in a Li-ion cell, with nm-scale interface sensitivity. O, F, and Si K-edge spectra, acquired as a function of potential, reveal when key reactions occur on high-capacity amorphous Si anodes cycled with and without fluoroethylene carbonate (FEC). The sequential formation of inorganic (LiF) and organic (-(C=O)O-) components is thereby revealed, and results in layering of the SEI. The addition of FEC leads to SEI formation at higher potentials which is implicated in the rapid healing of SEI defects and the improved cycling performance observed. Operando TEY-XAS offers new insights into the formation mechanisms of electrode-electrolyte interphases and their stability for a wide variety of electrode materials and electrolyte formulations.

6.
Adv Mater ; 34(37): e2204217, 2022 Sep.
Article in English | MEDLINE | ID: mdl-35866491

ABSTRACT

Ga2 O3 and its polymorphs are attracting increasing attention. The rich structural space of polymorphic oxide systems such as Ga2 O3 offers potential for electronic structure engineering, which is of particular interest for a range of applications, such as power electronics. γ-Ga2 O3 presents a particular challenge across synthesis, characterization, and theory due to its inherent disorder and resulting complex structure-electronic-structure relationship. Here, density functional theory is used in combination with a machine-learning approach to screen nearly one million potential structures, thereby developing a robust atomistic model of the γ-phase. Theoretical results are compared with surface and bulk sensitive soft and hard X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, spectroscopic ellipsometry, and photoluminescence excitation spectroscopy experiments representative of the occupied and unoccupied states of γ-Ga2 O3 . The first onset of strong absorption at room temperature is found at 5.1 eV from spectroscopic ellipsometry, which agrees well with the excitation maximum at 5.17 eV obtained by photoluminescence excitation spectroscopy, where the latter shifts to 5.33 eV at 5 K. This work presents a leap forward in the treatment of complex, disordered oxides and is a crucial step toward exploring how their electronic structure can be understood in terms of local coordination and overall structure.

7.
Faraday Discuss ; 236(0): 267-287, 2022 Aug 25.
Article in English | MEDLINE | ID: mdl-35543094

ABSTRACT

The key charge transfer processes in electrochemical energy storage devices occur at electrode-electrolyte interfaces, which are typically buried, making it challenging to access their interfacial chemistry. In the case of Li-ion batteries, metallic Li electrodes hold promise for increasing energy and power densities and, when used in conjunction with solid electrolytes, the adverse safety implications associated with dendrite formation in organic liquid electrolytes can potentially be overcome. To better understand the stability of solid electrolytes when in contact with alkali metals and the reactions that occur, here we consider the deposition of thin (∼10 nm) alkali metal films onto solid electrolyte surfaces, where the metal is thin enough that X-ray photoelectron spectroscopy can probe the buried electrode-electrolyte interface. We highlight the importance of in situ alkali metal deposition by assessing the contaminant species that are present after glovebox handling and the use of 'inert' transfer devices. Consequently, we compare and contrast three available methods for in situ alkali-metal deposition; Li sputter deposition, Li evaporation, and Li plating induced by e- flood-gun irradiation. Studies on both a sulphide solid electrolyte (Li6PS5Cl), and a single-layer graphene probe surface reveal that the more energetic Li deposition methods, such as sputtering, can induce surface damage and interfacial mixing that are not seen with thermal evaporation. This indicates that the appropriate selection of the Li deposition method for in situ studies is required to observe representative behaviour, and the results of previous studies involving energetic deposition may warrant further evaluation.

8.
ACS Appl Mater Interfaces ; 13(2): 2807-2819, 2021 Jan 20.
Article in English | MEDLINE | ID: mdl-33426870

ABSTRACT

The electronic and optical properties of (InxGa1-x)2O3 alloys are highly tunable, giving rise to a myriad of applications including transparent conductors, transparent electronics, and solar-blind ultraviolet photodetectors. Here, we investigate these properties for a high quality pulsed laser deposited film which possesses a lateral cation composition gradient (0.01 ≤ x ≤ 0.82) and three crystallographic phases (monoclinic, hexagonal, and bixbyite). The optical gaps over this composition range are determined, and only a weak optical gap bowing is found (b = 0.36 eV). The valence band edge evolution along with the change in the fundamental band gap over the composition gradient enables the surface space-charge properties to be probed. This is an important property when considering metal contact formation and heterojunctions for devices. A transition from surface electron accumulation to depletion occurs at x ∼ 0.35 as the film goes from the bixbyite In2O3 phase to the monoclinic ß-Ga2O3 phase. The electronic structure of the different phases is investigated by using density functional theory calculations and compared to the valence band X-ray photoemission spectra. Finally, the properties of these alloys, such as the n-type dopability of In2O3 and use of Ga2O3 as a solar-blind UV detector, are understood with respect to other common-cation compound semiconductors in terms of simple chemical trends of the band edge positions and the hydrostatic volume deformation potential.

9.
Nanoscale ; 12(43): 22234-22244, 2020 Nov 12.
Article in English | MEDLINE | ID: mdl-33141137

ABSTRACT

We find that the use of Au substrate allows fast, self-limited WS2 monolayer growth using a simple sequential exposure pattern of low cost, low toxicity precursors, namely tungsten hexacarbonyl and dimethylsulfide (DMS). We use this model reaction system to fingerprint the technologically important metal organic chemical vapour deposition process by operando X-ray photoelectron spectroscopy (XPS) to address the current lack of understanding of the underlying fundamental growth mechanisms for WS2 and related transition metal dichalcogenides. Au effectively promotes the sulfidation of W with simple organosulfides, enabling WS2 growth with low DMS pressure (<1 mbar) and a suppression of carbon contamination of as-grown WS2, which to date has been a major challenge with this precursor chemistry. Full WS2 coverage can be achieved by one exposure cycle of 10 minutes at 700 °C. We discuss our findings in the wider context of previous literature on heterogeneous catalysis, 2D crystal growth, and overlapping process technologies such as atomic layer deposition (ALD) and direct metal conversion, linking to future integrated manufacturing processes for transition metal dichalcogenide layers.

10.
Chem Mater ; 32(5): 1964-1973, 2020 Mar 10.
Article in English | MEDLINE | ID: mdl-32296264

ABSTRACT

Transparent conducting oxides (TCOs) are ubiquitous in modern consumer electronics. SnO2 is an earth abundant, cheaper alternative to In2O3 as a TCO. However, its performance in terms of mobilities and conductivities lags behind that of In2O3. On the basis of the recent discovery of mobility and conductivity enhancements in In2O3 from resonant dopants, we use a combination of state-of-the-art hybrid density functional theory calculations, high resolution photoelectron spectroscopy, and semiconductor statistics modeling to understand what is the optimal dopant to maximize performance of SnO2-based TCOs. We demonstrate that Ta is the optimal dopant for high performance SnO2, as it is a resonant dopant which is readily incorporated into SnO2 with the Ta 5d states sitting ∼1.4 eV above the conduction band minimum. Experimentally, the band edge electron effective mass of Ta doped SnO2 was shown to be 0.23m 0, compared to 0.29m 0 seen with conventional Sb doping, explaining its ability to yield higher mobilities and conductivities.

11.
Chem Mater ; 32(7): 3245-3253, 2020 Apr 14.
Article in English | MEDLINE | ID: mdl-32308255

ABSTRACT

The van der Waals material GeSe is a potential solar absorber, but its optoelectronic properties are not yet fully understood. Here, through a combined theoretical and experimental approach, the optoelectronic and structural properties of GeSe are determined. A fundamental absorption onset of 1.30 eV is found at room temperature, close to the optimum value according to the Shockley-Queisser detailed balance limit, in contrast to previous reports of an indirect fundamental transition of 1.10 eV. The measured absorption spectra and first-principles joint density of states are mutually consistent, both exhibiting an additional distinct onset ∼0.3 eV above the fundamental absorption edge. The band gap values obtained from first-principles calculations converge, as the level of theory and corresponding computational cost increases, to 1.33 eV from the quasiparticle self-consistent GW method, including the solution to the Bethe-Salpeter equation. This agrees with the 0 K value determined from temperature-dependent optical absorption measurements. Relaxed structures based on hybrid functionals reveal a direct fundamental transition in contrast to previous reports. The optoelectronic properties of GeSe are resolved with the system described as a direct semiconductor with a 1.30 eV room temperature band gap. The high level of agreement between experiment and theory encourages the application of this computational methodology to other van der Waals materials.

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