Spectroscopic observation of photo-induced metastable linkage isomers of coinage metal (Cu, Ag, Au) sulfur dioxide complexes

Liu, Xing; Wang, Xuefeng; Xu, Bing; Andrews, Lester

doi:10.1039/c3cp53811g

Cited by 14 publications

(30 citation statements)

References 76 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[ 36,37 ] Additionally, the existence of SO bonds was further confirmed by Fourier transform infrared spectroscopy with a peak observed at 1047 cm −1 assigned to the stretch of SO bond (Figure 2d; and Figure S8, Supporting Information). [ 38,39 ] Upon annealing, we notice a redistribution of spectral weight from the aforementioned two sulfur peaks indicative of CuS toward the two peaks at higher binding energy which we assign to the SO bonds. Apparently, the ratio of the SO bond increased from 15.25% to 40.73% after annealing (Table S2, Supporting Information).…”

Section: Resultsmentioning

confidence: 85%

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting

Zhang

Huang

Zhu

et al. 2021

Small

View full text Add to dashboard Cite

O 3 ), possessing a bandgap of 1.9-2.2 eV and theoretically enabling a photocurrent density of 12.6 mA cm −2 at 1.23 V versus reversible hydrogen electrode (RHE) for water splitting, [6] become one of the most investigated photoanode materials. Additionally, Hematite has stable properties, abundant reserves, and nontoxicity compared with other photoanode materials. [7] However, the photoelectrochemical performance of hematite is severely restricted by its short hole diffusion length (≈2-4 nm), low conductivity, and short lifetime of the excited state carriers (≈10 −12 s). Furthermore, a high concentration of surface states and slow kinetics for sluggish oxygen evolution reaction (OER) at the surface of Fe 2 O 3 call for the necessary modifications to improve the PEC performance.Cu 2 S, a p-type semiconductor with a narrow bandgap (1.2 eV), is attracting broad interest for solar energy conversion and storage in numerous applications. [8][9][10] It is ideally suitable for harvesting sunlight in a wide wavelength range and simultaneously the high conductivity allows for efficient photogenerated charge transfer. Moreover, copper vacancies are generated once copper(I) sulfide is exposed to oxygen, and then an localized surface plasmon resonance band will emerge. [11,12] This property of copper sulfide enables the utilization of sunlight with the wavelength up to the near-infrared region. Due to the photothermal effect, CuS compound nanocrystals have been used widely for energy storage and photothermal therapy. [13,14] Importantly, a recent report demonstrates that the derivatives of Cu 2 S under the condition of OER The severe charge recombination and the sluggish kinetic for oxygen evolution reaction have largely limited the application of hematite (α-Fe 2 O 3 ) for water splitting. Herein, the construction of Cu 2 S/Fe 2 O 3 heterojunction and discover that the formation of covalent SO bonds between Cu 2 S and Fe 2 O 3 can significantly improve the photoelectrochemical performance and stability for water splitting is reported. Compared with bare Fe 2 O 3 , the heterostructure of Cu 2 S/Fe 2 O 3 endows the resulting electrode with enhanced charge separation and transfer, extended range for light absorption, and reduced charge recombination rate. Additionally, due to the photothermal properties of Cu 2 S, the heterostructure exhibits locally a higher temperature under illumination, profitable for increasing the rate of oxygen evolution reaction. Consequently, the photocurrent density of the heterostructure is enhanced by 177% to be 1.19 mA cm −2 at 1.23 V versus reversible hydrogen electrode. This work may provide guideline for future in the design and fabrication of highly efficient photoelectrodes for various reactions.

show abstract

Section: Resultsmentioning

confidence: 85%

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting

Zhang

Huang

Zhu

et al. 2021

Small

View full text Add to dashboard Cite

show abstract

“…Using a mixed H 2 S+HDS+D 2 S sample, three triplet band distributions were observed in upper Ta The 1796.4 and 1780.7 cm −1 absorptions in the Ta+H 2 S experiments are assigned to H 2 Ta(SH) 2 molecule. Two bands increased on annealing to 25 K, slightly decreased on full-arc photolysis and increased again on annealing to 30 K. These two bands showed no sulfur- 34 Similarly in the Ta+H 2 S experiment a new Ta−H stretching frequency at 1759.0 cm −1 was observed, which shifted to 1260.5 cm −1 , defying 1.3955 H/D ratio. The triatomic molecule HMS (M=Zr, Hf) comes into mind for these band assignment though the M−S stretching frequencies are missing.…”

Section: H2tas and H2ta(sh)2mentioning

confidence: 88%

“…HMSH can also further react with other sulfur hydride to form the H 2 M(SH) 2 molecules. The molecules were identified on the basis of the D 2 S and H 2 34 S isotopic substitutions as well as density functional calculations. Qualitative analysis of the reaction paths leading to the observed products was proposed.…”

Section: Discussionmentioning

confidence: 99%

“…Our experimental method has been described in detail previously [32][33][34]. Briefly, a Nd:YAG laser fundamental (1064 nm, 10 Hz repetition rate with 10 ns pulse width) was focused onto a rotating transition metal target through a hole in a CsI window cooled normally to 4 K by means of a closed-cycle helium refrigerator.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…In the V+H 2 S experiment a weak band in V−S stretching region at 529.4 cm −1 is due to diatomic VS molecule, which was observed on deposition and greatly enhanced on broad band photolysis at the expense of HVSH and H 2 V(SH) 2 molecules. This band exhibited no deuterium isotopic shift but shifted to 519.7 cm −1 with H 2 34 S, and gave an isotopic 32 S/ 34 S ratio of 1.0187.…”

Section: Vs and Vs2mentioning

confidence: 98%

See 2 more Smart Citations

Reactions of Group V Metal Atoms with Hydrogen Sulfide: Argon Matrix Infrared Spectra and Theoretical Calculations

Zhao¹,

Xu²,

Yu³

et al. 2016

Chinese Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H−S bond of H 2 S to form the HMSH molecules (M=V, Nb, Ta), which rearranged to H 2 MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H 2 S to form the H 2 M(SH) 2 molecules. These new molecules were identified on the basis of the D 2 S and H 2 34 S isotopic substitutions. DFT (B3LYP and BPW91) theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS+H 2 on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.

show abstract

Photosensitive Tin Sulfur Dioxide Complexes with Unexpected Bonding Modes

Liu

2019

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Infrared spectra of the matrix‐isolated Sn(η2‐O2S), Sn(η2‐OSO), Sn(η2‐O2S)(η1‐OSO), Sn(η2‐O2S)2, OSn2(η2‐SO), and Sn(μ2‐O2)SnS molecules were observed following laser‐ablated Sn atom reactions with SO2 during condensation in solid argon. The assignments for the major vibrational modes were confirmed by appropriate S18O2 and 34SO2 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). Interestingly, the mononuclear complexes are interconvertible; that is, irradiation induces the isomerization of Sn(η2‐O2S) and Sn(η2‐O2S)(η1‐OSO) to Sn(η2‐OSO) and Sn(η2‐O2S)2, respectively, and vice versa on annealing. However, there is no evidence of isomerization reaction in between the binuclear molecules OSn2(η2‐SO) and Sn(μ2‐O2)SnS. Bonding in these products is discussed, and the electronic structure changes associated with different bonding types are revealed, which is crucial for the observed photochemical reactions.

show abstract

Spectroscopic observation of photo-induced metastable linkage isomers of coinage metal (Cu, Ag, Au) sulfur dioxide complexes

Cited by 14 publications

References 76 publications

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting

Reactions of Group V Metal Atoms with Hydrogen Sulfide: Argon Matrix Infrared Spectra and Theoretical Calculations

Photosensitive Tin Sulfur Dioxide Complexes with Unexpected Bonding Modes

Contact Info

Product

Resources

About

Spectroscopic observation of photo-induced metastable linkage isomers of coinage metal (Cu, Ag, Au) sulfur dioxide complexes

Cited by 14 publications

References 76 publications

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu2S/Fe2O3 Heterojunction for Water Splitting

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu2S/Fe2O3 Heterojunction for Water Splitting

Reactions of Group V Metal Atoms with Hydrogen Sulfide: Argon Matrix Infrared Spectra and Theoretical Calculations

Photosensitive Tin Sulfur Dioxide Complexes with Unexpected Bonding Modes

Contact Info

Product

Resources

About

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting

Covalent SO Bonding Enables Enhanced Photoelectrochemical Performance of Cu₂S/Fe₂O₃ Heterojunction for Water Splitting