Deposition of Gold Particles on Mesoporous Catalyst Supports by Sonochemical Method, and their Catalytic Performance for CO Oxidation

Supported gold catalysts on the mesoporous (MSP) metal oxides were prepared by a one-step, ultrasound-assisted reduction method, and characterized by XRD, HRTEM, EDX, BET, and XPS analysis. Their catalytic activities were examined in the oxidation of CO. Compared to the Au/Fe₂O₃(MSP) catalyst, the Au/TiO₂(MSP) and Au/Fe₂O₃-TiO₂(MSP) catalysts exhibited higher catalytic activity in the oxidation of CO at low temperatures. The high catalytic activity of Au/TiO₂(MSP) was attributed to the metallic state of the gold nanoparticles, their small size (2–2.5 nm), and their high dispersion on the catalyst support.     

Growth of Ag and Au Nanoparticles on Reduced and Oxidized Rutile TiO2(110) Surfaces

The nucleation and growth of Au and Ag nanoparticles on rutile TiO₂(110)–(1 × 1) surfaces in different oxidation states is studied by means of photoelectron spectroscopy (PES) and scanning tunneling microscopy (STM). Au and Ag nanoparticles were found to bind much more strongly to oxidized TiO₂(110) model supports than to reduced TiO₂(110) surfaces, as directly revealed by STM. Detailed PES studies addressing small Au and Ag particles complete this picture and show that the PES core level spectra acquired on Au/TiO₂(110) and Ag/TiO₂(110) can be best described by fitting with two binding energy (BE) components. Particularly for coverages in the sub-monolayer regime and for depositions at low temperatures (100 K) the PES core level spectra must be fitted with at least two BE components. The higher BE component is attributed to atoms at the interface between the metal clusters and the TiO₂(110) support. For Au/TiO₂(110), the two BE components were evident in the core level spectra for higher coverage than for Ag/TiO₂(110), consistent with different growth modes for Au (initially 2D) and Ag (3D) on TiO₂(110). Finally, strong evidence for charge transfer from Ag nanoparticles to the TiO₂(110) support is presented, whereas the charge transfer between Au nanoparticles and the TiO₂(110) support is very small.     

Chemical vapor deposition of gold on Al2O3, SiO2, and TiO2 for the oxidation of CO and of H2

In order to clarify the effect of metal oxide support on the catalytic activity of gold for CO oxidation, gold has been deposited on SiO₂ with high dispersion by chemical vapor deposition (CVD) of an organo-gold complex. Comparison of Au/SiO₂ with Au/Al₂O₃ and Au/TiO₂, which were prepared by both CVD and liquid phase methods, showed that there were no appreciable differences in their catalytic activities as far as gold is deposited as nanoparticles with strong interaction. The perimeter interface around gold particles in contact with the metal oxide supports appears to be essential for the genesis of high catalytic activities at low temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of metal–cadmium sulfide nanocomposites using jingle-bell-shaped core-shell photocatalyst particles

Photocatalytic deposition of gold (Au) and silver (Ag) nanoparticles was investigated using jingle-bell-shaped silica (SiO₂)-coated cadmium sulfide (CdS) nanoparticles (SiO₂/CdS), which each had a void space between the CdS core and SiO₂ shell, as a photocatalyst. A size-selective photoetching technique was used to prepare the jingle bell nanostructure of SiO₂/CdS. Nanoparticles of Au and Ag were deposited by irradiation of the photoetched SiO₂/CdS in the presence of the corresponding metal complexes under deaerated conditions. Chemical etching of Au-deposited particles enabled the selective removal of CdS without any influence on the surface-plasmon absorption of Au. TEM analyses of the resulting particles suggested that some particles were encapsulated in hollow SiO₂ particles, while other Au particles were deposited on the outer surface of the SiO₂ shell. Emission spectra of the photoetched SiO₂/CdS showed that the metal deposition developed a broad emission with a peak around 650 nm originating from surface defect sites, the degree being dependent on the kind of metal nanoparticles and their amount of deposition. This fact can be explained by the formation of metal–CdS binary nanoparticles having defect sites at the interface between metal and CdS.     

Photocatalytic Preparation of Encapsulated Gold Nanoparticles by Jingle-bell-shaped Cadmium Sulfide–silica Nanoparticles

Gold (Au) nanoparticles were deposited inside silica: (SiO₂) shells containing cadmium sulfide (CdS) nanoparticles through photocatalytic reduction of potassium dicyanogold(I) by CdS. Photocatalytic Au deposition occurred only when core-shell nanoparticles having a void space between the core and shell, i.e., a jingle-bell-shaped structure, were used. These core-shell nanoparticles were prepared by size-selective photoetching of SiO₂ -covered CdS nanoparticles. The size of Au nanoparticles could be controlled by adjustment of the void space in SiO₂-covered CdS. Dissolution of CdS by acid treatment from the Au-deposited jingle-bell nanoparticles did not have any effect on the surface-plasmon absorption by Au. These facts indicate that Au nanoparticles of adjustable size can be prepared in an SiO₂ shell that prevents mutual coalescence of Au nanoparticles but allows permeation of molecules and ions.     

The Nanoscience Revolution: Merging of Colloid Science, Catalysis and Nanoelectronics

The incorporation of nanosciences into catalysis studies has become the most powerful approach to understanding reaction mechanisms of industrial catalysts and designing new-generation catalysts with high selectivity. Nanoparticle catalysts were synthesized via controlled colloid chemistry routes. Nanostructured catalysts such as nanodots and nanowires were fabricated with nanolithography techniques. Catalytic selectivity is dominated by several complex factors including the interface between active catalyst phase and oxide support, particle size and surface structure, and selective blocking of surface sites, etc. The advantage of incorporating nanosciences into the studies of catalytic selectivity is the capability of separating these complex factors and studying them one by one in different catalyst systems. The role of oxide–metal interfaces in catalytic reactions was investigated by detection of continuous hot electron flow in catalytic nanodiodes fabricated with shadow mask deposition technique. We found that the generation mechanism of hot electrons detected in Pt/TiO₂ nanodiode is closely correlated with the turnover rate under CO oxidation. The correlation suggests the possibility of promoting catalytic selectivity by precisely controlling hot electron flow at the oxide–metal interface. Catalytic activity of 1.7–7.2 nm monodispersed Pt nanoparticles exhibits particle size dependence, demonstrating the enhancement of catalytic selectivity via controlling the size of catalyst. Pt–Au alloys with different Au coverage grown on Pt(111) single crystal surface have different catalytic selectivity for four conversion channels of n-hexane, showing that selective blocking of catalytic sites is an approach to tuning catalytic selectivity. In addition, presence and absence of excess hydrogen lead to different catalytic selectivity for isomerization and dehydrocyclization of n-hexane on Pt(111) single crystal surface, suggesting that modification of reactive intermediates by the presence of coadsorbed hydrogen is one approach to shaping catalytic selectivity. Several challenges such as imaging the mobility of adsorbed molecules during catalytic reactions by high pressure STM and removing polymeric capping agents from metal nanoparticles remain.     

Reactivity and sintering kinetics of Au/TiO2(110) model catalysts: particle size effects

We review here our studies of the reactivity and sintering kinetics of model catalysts consisting of gold nanoparticles dispersed on TiO₂(110). First, the nucleation and growth of vapor-deposited gold on this surface was experimentally examined using x-ray photoelectron spectroscopy and low energy ion scattering. Gold initially grows as two-dimensional islands up to a critical coverage, θ _cr, after which 3D gold nanoparticles grow. The results at different temperatures are fitted well with a kinetic model, which includes various energetic parameters for Au adatom migration. Oxygen was dosed onto the resulting gold nanoparticles using a hot filament technique. The desorption energy of O_a was examined using temperature programmed desorption (TPD). The O_a is bonded ~40% more strongly to smaller (thinner) Au islands. Gaseous CO reacts rapidly with this O_a to make CO₂, probably via adsorbed CO. The reactivity of O_a with CO increases with increasing particle size, as expected based on Br?nsted relations. Propene adsorption leads to TPD peaks for three different molecularly adsorbed states on Au/TiO₂(110), corresponding to propene adsorbed on gold islands, to Ti sites on the substrate, and to the perimeter of gold islands, with adsorption energies of 40, 52 and 73 kJ/mol, respectively. Thermal sintering of the gold nanoparticles was explored using temperature-programmed low-energy ion scattering. These sintering rates for a range of Au loadings at temperatures from 200 to 700 K were well fitted by a theoretical model which takes into consideration the dramatic effect of particle size on metal chemical potential using a modified bond additivity model. When extrapolated to simulate isothermal sintering at 700 K for 1 year, the resulting particle size distribution becomes very narrow. These results question claims that the shape of particle size distributions reveal their sintering mechanisms. They also suggest why the growth of colloidal nanoparticles in liquid solutions can result in very narrow particle size distributions.     

Formation of gold nanoparticles on multiwalled carbon nanotubes by thermal evaporation

Multiwalled carbon nanotubes (MWCNTs) were grown on W substrates by chemical vapor deposition and modified with Au nanoparticles by thermal evaporation. The resulting hybrid structures were investigated by TEM to determine the effects of evaporation rate, nominal film thickness, and substrate temperature on the nanoparticle size and distribution. The results demonstrate that as-grown MWCNTs can be used as a support for well distributed Au nanoparticles, with the size and distribution on the carbon nanotubes being primarily influenced by the nominal film thickness. The observed structures ranged from small 4 nm diameter spherical particles to 150 nm long wire-like structures. Depositions with substrates at 25 °C and 400 °C resulted in similar particle structures, except for the highest amount of deposited Au.     

Electrocatalytic properties of Pd clusters on Au nanoparticles in formic acid electro-oxidation

Pd clusters were formed on highly dispersed Au nanoparticles (∼3.5 nm in diameter) using a seed-mediated growth process. The structural information and electrocatalytic activities of these Pd clusters on Au nanoparticles were confirmed by high-resolution-transmission-electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The resulting nanoparticles, which had a uniform size (<5 nm in diameter), were highly dispersed on carbon particles, and Pd clusters (<0.44 nm in size, <2 atomic layers) were formed selectively on Au nanoparticles. XPS results show that the Pd 3d_5/2 peak shifted to lower binding energies and that the amount of surface oxide decreased as the Pd content was decreased on the Au nanoparticles. In formic acid electro-oxidation, these Pd clusters exhibit enhanced electrocatalytic activity relative to that of carbon-supported Pd nanoparticles. These results may be due to the modified electronic and geometric structure of the Pd clusters on the Au nanoparticle substrate.     

Photocatalytic H2 Production from Ethanol–Water Mixtures Over Pt/TiO2 and Au/TiO2 Photocatalysts: A Comparative Study

Pt/TiO₂ (Pt loadings 0–4 wt%) and Au/TiO₂ (Au loadings 0–4 wt%) photocatalysts were synthesized, characterized and tested for H₂ production from ethanol–water mixtures (80 vol% ethanol, 20 vol% H₂O) under UV excitation. Average metal nanoparticle sizes determined by TEM were 1–3 nm for Pt in the Pt/TiO₂ photocatalysts and 5–7 nm for Au in the Au/TiO₂ photocatalysts. Au/TiO₂ showed an intense localized surface plasmon resonance feature at ~570 nm, typical for metallic Au nanoparticles of diameter ~5 nm supported on TiO₂. X-ray photoelectron spectroscopy and X-ray diffraction analyses established that Pt and Au were present in metallic form on the TiO₂ support. X-ray fluorescence revealed close accord between nominal and actual Pt and Au loadings. The Au/TiO₂ and Pt/TiO₂ photocatalysts both displayed very high activities for H₂ production under UV irradiation, with the Au/TiO₂ samples affording slightly superior rates of H₂ production at most metal loadings. The 2 wt% Au/TiO₂ and 1 wt% Pt/TiO₂ photocatalysts showed the highest H₂ production rates (32–34 mmol g^?1 h^?1). Photoluminescence studies confirmed that Pt and Au nanoparticles positively enhance the photocatalytic properties of P25 TiO₂ for H₂ production by acting as electron acceptors and thereby suppressing electron–hole pair recombination in TiO₂.     

Gold nanoparticle formation using Shewanella oneidensis: a fast biosorption and slow reduction process

BACKGROUND: The metal respiring bacterium Shewanella oneidensis has previously been used for reduction of Pd(II) into Pd(0) nanoparticles. This study investigated whether Shewanella oneidensis could also perform the reduction of Au(III) to Au(0). The kinetics of both the biosorption and reduction of Au(III) were studied. RESULTS: Biosorption of Au(III) was a fast and efficient process, and depended on the presence of an electron donor, the pH and the medium used. The reduction process, however, appeared to be a slow process, requiring the presence of an electron donor. As reduction also occurred in heat‐killed cells, it is suggested that the reduction is non‐enzymatic. At a concentration of 100 mg L^?1 Au(III), the nanoparticles were mainly smaller than 10 nm and precipitated intracellularly. With H₂ as the electron donor, it was shown that the location of the particles and the size could be steered by changing the concentration of Au(III). CONCLUSIONS: After a fast biosorption and slow reduction process, Au(0)‐nanoparticles were formed inside the cells or on the cell wall of Shewanella oneidensis. In most cases, these particles had interesting properties, such as small size and a narrow size distribution, which can make them suitable for applications in, for example, catalysis. Copyright © 2010 Society of Chemical Industry     

Au/MnO2–TiO2 catalyst for preferential oxidation of carbon monoxide in hydrogen stream

The catalytic activity of nanosize gold catalysts supported on MnO₂–TiO₂ and prepared by deposition–precipitation method has been investigated for preferential oxidation of carbon monoxide in H₂ stream. The catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, nitrogen sorption, transmission electron microscopy, and X-ray photoelectron spectroscopy. The influence of pH in the preparation process and the amount of MnO₂ loading on the catalytic properties of the Au/MnO₂–TiO₂ catalysts were also studied. Fine dispersion of gold nanoparticles on all the supports was obtained. Especially, Au/MnO₂–TiO₂ with MnO₂/TiO₂ mol ratio of 2:98, showed a mean Au particle size of 2.37 nm. The nanosized support constrained the size of gold. The addition of MnO₂ on Au/TiO₂ catalyst improved the selectivity of CO oxidation without sacrificing CO conversion in hydrogen stream between 50 and 100 °C. This could be attributed to the interactions of gold metal with MnO₂–TiO₂ support and the optimum combination of metallic and electron-deficient gold on the catalyst surface.     

Performance of Gold Nanoparticles Supported on Carbon Nanotubes for Selective Oxidation of Cyclooctene with Use of O2 and TBHP

Gold nanoparticles supported on multi-walled carbon nanotubes (Au/CNTs) were developed for the selective epoxidation of cyclooctene with oxygen and small amount of tert-butyl hydroperoxide (O₂-TBHP). We found that the Au/CNTs could provide the best combination of selectivity and conversion in comparison with the supported gold catalysts with several other carriers like active carbon, graphite, TiO₂, SiO₂ and Al₂O₃. The conversion of cyclooctene and the selectivity to epoxide increased with the amount of TBHP, but both reached almost maxima when the TBHP amount was higher than 5.0 mol% of cyclooctene. The CNTs-supported gold nanoparticles with mean sizes ranging from 3.1 to 15.0 nm could be prepared by using sol-immobilization method. The Au/CNTs catalysts with smaller gold particle size were related to higher epoxide yield, indicating a size effect of gold nanoparticles on the catalytic performance. The results suggested that the epoxidation of cyclooctene over the Au/CNTs with use of O₂-TBHP would be structure-sensitive.     

Self-assembled fabrication of a polycrystalline boron-doped diamond surface supporting Pt (or Pd)/Au-shell/core nanoparticles on the (111) facets and Au nanoparticles on the (100) facets

Modified boron-doped diamond (BDD) surfaces supporting different, carefully selected types of metal nanoparticles on different types of crystal facets were fabricated via a self-assembly method. A hydrogen plasma-treated BDD surface was treated with UV/ozone for 10 s followed by immersion in a Au nanoparticle (AuNP) solution to fabricate a BDD surface selectively and densely supporting AuNPs on the (111) facet (AuNP₁₁₁-BDD). The AuNP₁₁₁-BDD sample was then immersed in H₂PtCl₆/ascorbic acid or H₂PdCl₄/sodium citrate to cover the AuNP surface with Pt or Pd (Pt/AuNP₁₁₁-BDD or Pd/AuNP₁₁₁-BDD). These samples were treated with UV/ozone for 40 s followed by re-immersion in the AuNP solution to immobilize AuNPs on the (100) facets (Pt/AuNP₁₁₁-AuNP₁₀₀-BDD or Pd/AuNP₁₁₁-AuNP₁₀₀-BDD). The metal nanoparticles supported on the BDD surface were confirmed by cyclic voltammetry to be electrochemically active. The crystal-facet-selective support of the metal nanoparticles was also confirmed by two-dimensional elemental mapping via field emission Auger electron spectroscopy. The macro procedures used for the crystal-facet-selective immobilization of the AuNPs was reproducible, and this technique should be applicable to the creation of a new class of advanced materials in such fields as optics, electronics, sensing, and (electro)catalysis.     

CO Oxidation of Au–Pt Nanostructures: Enhancement of Catalytic Activity of Pt Nanoparticles by Au

The CO oxidation activity of Pt deposited on Ta₂O₅/Ta was studied with various amounts of Au post-deposited on Pt/Ta₂O₅/Ta. For Pt nanoparticles with a mean size of 2–4 nm, an enhancement in the CO oxidation activity with increasing amount of post-deposited Au was found. The mixed Au–Pt nanoparticles with sizes in the range of 2–4 nm exhibited higher stability than the bare Au nanoparticles with a similar size range. In contrast to the results obtained with the Pt nanoparticles, the catalytic activity of a thicker Pt film gradually decreased with increasing amount of Au deposited. Based on the CO desorption experiments, it is suggested that the surface of the catalytically active Au–Pt bimetallic structures consists of both Au and Pt sites.     

Microwave-Assisted Base-Free Oxidation of Glucose with H2O2 on Gold- and Manganese-Containing SBA-15—Insight into Factors Affecting the Reaction Pathway

The aim of this work was to gain insights into the role of manganese in MnSBA-15 support for gold in the base-free glucose oxidation with H₂O₂ using a microwave reactor. MnSBA-15 (manganese—acidity source) and SBA-15 (for comparison) were modified with Au (2.2 wt. %) and Cu (for comparison). The physicochemical properties of the catalysts were investigated by XRD, N₂ ads/des, TEM, UV-vis, XPS, pyridine adsorption combined with FTIR, ATR-FTIR, and 2-propanol decomposition. The effects of the Mn presence in the support, Au NPs size that determines the number of active Au centers, and the Fermi energy (E_F), together with the effects of the pore size, reaction temperature, and time on the activity and selectivity of the applied catalysts were assessed and discussed. It has been demonstrated that the presence of Mn generated Lewis acid centers which did not participate in glucose and H₂O₂ adsorption, and thus, were not directly involved in the reaction pathway. Both reagents were adsorbed on gold nanoparticles. H₂O₂ was decomposed to molecular oxygen which oxidized glucose to gluconic acid (50–90% of glucose conversion depending on the reaction time and ~100% selectivity). The presence of manganese in MnSBA-15 was responsible for increased Au NPs size and only slightly influenced the negative charge on gold particles. To achieve effective activity a compromise between the number of active gold species and the level of E_F has to be reached (for 5.7 nm Au NPs).     

Hydroxyls-induced oxygen activation on “inert” Au nanoparticles for low-temperature CO oxidation

The NaOH additive substantially enhances the catalytic activity of Au/SiO₂ catalyst inert in catalyzing CO oxidation at temperatures below 150 °C, and Au/NaOH/SiO₂ catalyst with a NaOH:Au atomic ratio of 6 is active at room temperature. Both the particle size distribution and the electronic structure of Au nanoparticles were found to be similar in Au/SiO₂ and Au/NaOH/SiO₂ catalysts, unambiguously proving that hydroxyls on “inert” Au nanoparticles can induce the activation of O₂ for CO oxidation at room temperature. The accompanying density functional theory (DFT) calculation results reveal the determining role of COOH(a) in hydroxyls-induced activation of O₂ on the Au(1 1 1) surface. Our results successfully elucidate the influence of hydroxyls on the intrinsic activity of Au nanoparticles in CO oxidation, providing novel insights into the role of hydroxyls in the catalytic activity of Au catalysts and advancing the fundamental understanding of oxidation reactions catalyzed by Au catalysts.     

Fabrication of polyoxometallate-modified gold nanoparticles and their utilization as supports for dispersed platinum in electrocatalysis

The usefulness of Keggin-type anions (PMo₁₂O₄₀³⁻) as both reducing, capping and activating agents during synthesis of polyoxometallate-modified gold nanoparticles is demonstrated here. Fabrication of gold nanoparticles stabilized with monolayer-type films of inorganic polyoxometallates (e.g. phosphododecamolybdates), Au-PMo₁₂, was achieved by treating an aqueous solution of gold precursor (HAuCl₄) with a solution of the partially reduced heteropolyblue molybdate. The choice of temperature strongly affected morphology and size of the resulting Au nanoparticles. The presence of strongly adsorbed molybdate-agents on surfaces of gold nanoparticles was evident from the independent infrared (FTIR by reflectance) and voltammetric experiments. Interfacial polymolybdate anions on Au prevent the particle agglomeration and support formation of the stable colloidal Au-PMo₁₂ solutions. They are colored due to existence of the plasmonic effect. The Au-PMo₁₂ nanoparticles typically had 30–40 nm diameters, and they were used as supports or carriers for dispersed catalytic platinum nanoparticles (of ca. 7–8 nm diameters). Polyoxometallates (PMo₁₂O₄₀³⁻) existing on gold surfaces could also interact with neighboring platinum centers thus acting as “linking” agents facilitating dispersion of Pt nanoparticles. Further, the phosphomolybdate adsorbates (on Au supports) are also likely to activate Pt sites (e.g. by providing reactive hydroxy groups) towards more efficient electrocatalytic oxidation of ethanol both under voltammetric and chronoamperometric conditions.     

Crystallinity dynamics of gold nanoparticles during sintering or coalescence

The crystallinity of gold nanoparticles during coalescence or sintering is investigated by molecular dynamics. The method is validated by the attainment of the Au melting temperature that increases with increasing particle size approaching the Au melting point. The morphology and crystal dynamics of nanoparticles of (un)equal size during sintering are elucidated. The characteristic sintering time of particle pairs is determined by tracing their surface area evolution during coalescence. The crystallinity is quantified by the disorder variable indicating the system's degree of disorder. The atoms at the grain boundaries are amorphous, especially during particle adhesion and during sintering when grains of different orientation are formed. Initial grain orientation affects final particle morphology leading to exposure of different crystal surfaces that can affect the performance of Au nanoparticles (e.g., catalytic efficiency). Coalescence between crystalline and amorphous nanoparticles of different size results in polycrystalline particles of increasing crystallinity with time and temperature. Crystallinity affects the sintering rate and mechanism. Such simulations of free‐standing Au nanoparticle coalescence are relevant also to Au nanoparticles on supports that do not exhibit strong affinity or strong metal support interactions. © 2015 American Institute of Chemical Engineers AIChE J, 62: 589–598, 2016     

Desulfurization Reactions on Surfaces of Metal Carbides: Photoemission and Density–Functional Studies

High-resolution photoemission and density functional (DF) calculations were used to study the interaction of atomic sulfur and S-containing molecules with metal carbides in which the carbon/metal ratio varies from 0.5 to 1 (M₂C and MC, M = Ti, V or Mo). In these compounds, the C sites cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates. For example, the adsorption of S on TiC(001) induces a large positive shift (1.0–1.3 eV) in the C 1s core level. DF calculations give a CTiTi hollow as the most stable site for the S adatoms. There is a correlation between the adsorption energy of S or thiophene and shifts in the centroid of the metal d band induced by metal–carbon bonding in the metal carbides. The M₂C and MC carbides have difficulty obeying Sabatier’s principle for being good HDS catalysts because some of them interact too strongly with the products (M₂C stoichiometry) and the others have problems dissociating the reactants (MC stoichiometry). The addition of small Au nanoparticles is an efficient way for enhancing the HDS activity of MC catalysts. In spite of the very poor desulfurization performance of TiC and MoC, the Au/TiC and Au/MoC systems display an HDS activity comparable or higher than that of conventional Ni/MoS _x catalysts. The Au nanoparticles probably increase the HDS activity of the metal carbides by enhancing the adsorption energy of thiophene and by helping in the dissociation of H₂ to produce the hydrogen necessary for the hydrogenolysis of C–S bonds and the removal of sulfur.