Au Catalysts Research Articles

Gold-catalyzed endo-selective Ring-opening of Epoxides and its Application in Construction of Poly-ethers.

Tetrahydropyran and tetrahydropyran-fused poly-ethers scaffolds are found in many classes of natural products and medicinally relevant small molecules. Here we describe a catalytic system for 6-endo selective ring-opening of epoxides by Au(I) or Au(III) catalyst that provides rapid access to various tetrahydropyran-derived motifs. It also could efficiently construct the subunits of marine ladder-like poly-ethers through emulating the Nakanishi's hypothesis on the biosynthesis of these toxins. The synthetic utility of this method is also demonstrated in the preparation of the tricyclic core of tetrahydropyran-containing macrolide natural products lituarines A-C.

Distinct Site Motifs Activate O2 and H2 on Supported Au Nanoparticles in Liquid Water.

Au nanoparticles catalyze the activation and conversion of small molecules with rates and kinetic barriers that depend on the dimensions of the nanoparticle, composition of the support, and presence of catalytically culpable water molecules that solvate these interfaces. Here, molecular interpretations of steady-state rate measurements, kinetic isotope effects, and structural characterizations reveal how the interface of Au nanoparticles, liquid water, and metal oxide supports mediate the kinetically relevant activation of H2 and sequential reduction of O2-derived intermediates during the formation of H2O2 and H2O. Rates of H2 consumption are 10-100 fold greater on Au nanoparticles supported on metal oxides (e.g., titania) compared to more inert and hydrophobic materials (carbon, boron nitride). Similarly, Au nanoparticles on reducible and Lewis acidic supports (e.g., lanthana) bind dioxygen intermediates more strongly and present lower barriers (<22 kJ mol-1) for O-O bond dissociation than inert interfaces formed with silica (>70 kJ mol-1). Selectivities for H2O2 formation increase significantly as the diameters of the Au nanoparticles increase because differences in nanoparticle size change the relative fractions of exposed sites that exist at Au-support interfaces. In contrast, site-normalized rates and barriers for H2 activation depend weakly on the size of Au nanoparticles and the associated differences in active site motifs. These findings suggest that H2O aids the activation of H2 at sites present across all surface Au atoms when nanoparticles are solvated by water. However, molecular O2 preferentially binds and dissociates at Au-support interfaces, leading to greater structure sensitivity for barriers of O-O dissociation across different support identities and sizes of Au nanoparticles. These insights differ from prior knowledge from studies of gas-phase reactions of H2 and O2 upon Au nanoparticle catalysts within dilute vapor pressures of water (10-4 to 0.1 kPa H2O), in which catalysis occurs at the perimeter of the Au-support interface. In contrast, contacting Au catalysts with liquid water (55.5 M H2O) expands catalysis to all surface Au atoms and enables appreciable H2O2 formation.

Key Role of Cations in Stabilizing Hydrogen Radicals for CO2-to-CO Conversion via a Reverse Water-Gas Shift Reaction.

Electrochemically converting CO2 into valuable chemicals and fuels in acidic media is argued as a promising energy- and carbon-efficient route. Although several key roles of alkali cations have been unveiled, the alkali cation trends for CO2 reduction remain largely elusive. With decreasing cation size from Cs+ to Li+, here we show that the apparent proton diffusion coefficient in 3.0 M Li+ is tens-fold lower than in 3.0 M K+ and 3.0 M Cs+ acidic electrolytes. Although Li+ has the strongest inhibition ability for proton transport, it acts the worst for both the CO2-to-CO conversion and partial current density on Au catalysts. Unexpectedly, K+ with a higher proton transport performs the best for CO2-to-CO conversion. We thus revisit the roles of alkali cations and find that hydrated K+ can stabilize hydrogen radicals benefiting CO2 conversion at the electrode interface while for Li+ this is not the case. This study proposes that cation-stabilized atomic hydrogen assists in activating CO2 via a reverse water-gas shift route under electrochemical conditions.

Controlled synthesis of reduced graphene oxide-supported bimetallic Pt–Au nanoparticles for enhanced electrooxidation of methanol

Controlled construction of bimetallic interfaces on conductive carbon supports is extremely important for achieving better synergistic effect required for electrooxidation of small organic molecules for energy applications. Herein, controlled synthesis of reduced graphene oxide (RGO)-supported bimetallic Pt–Au nanoparticles (Pt–Au/RGO) for electrooxidation of methanol using a facile and practical approach was described. By carefully adapting sequential and simultaneous reduction steps H2PtCl6 and AuCl3were reduced on RGO support using ammonia borane (AB) and ascorbic acid (AA) as reducing agents. Three types of Pt–Au/RGO catalysts were prepared and labeled as PtAu/RGO-AB1, PtAu/RGO-AB, and PtAu/RGO-AA. The reduction process was carried at ambient conditions, without the use of surfactants, and the catalysts obtained were analyzed through various techniques, including X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). The PtAu/RGO-AB1 catalyst showed remarkable uniformity on the RGO sheets, with an average particle size of 2–3 nm. The electrochemical behavior of Pt–Au catalysts supported on reduced graphene oxide (RGO) for methanol oxidation was systematically investigated via cyclic voltammetry and chronoamperometry techniques. Among the studied catalysts, PtAu/RGO-AB1 exhibited high electrochemical active surface area (ECSA) of 92.47 m2/g, along with the highest mass and ECSA-normalized activities for the electrooxidation of methanol. PtAu/RGO-AB1 manifested exceptional resistance to accumulated CO-like species, as evidenced by its higher forward peak current density to reverse peak current density ratio (If/Ib) of 2.20. The facile and effective synthesis strategy described here provides a promising method for fabricating well-defined multi-component nanostructured electrocatalysts with potential applications for various fuel cell reactions.

Oxidative Cleavage of 9,10-Dihydroxystearic Acid on Supported Au, Pd and PdAu Nanoparticle-Based Catalysts

The oxidative C-C cleavage of a C18 substrate is an important transformation in synthetic organic chemistry, facilitating the synthesis of valuable C8-C9 acids widely used in many industries. Through a comparative analysis of the catalytic and physicochemical properties of catalysts, comprising mono- (Pd or Au) and bimetallic (PdAu) nanoparticles deposited on oxides, oxyhydroxides and graphite-like carbon material Sibunit (Cp), it was shown that the efficiency of the catalyst in the oxidative cleavage of 9,10-dihydroxystearic acid relies on the nature of the active component, the support and the average size of metal nanoparticles (NPs). The dependency of 9,10-DSA conversion on the average size of metal NPs shows the structural sensitivity of the oxidative cleavage reaction. Notably, catalysts with an average size of gold particles less than 3 nm exhibit the highest activity. The nature of the active component and the support material are crucial factors determining the process selectivity. Among the catalysts studied, the most effective for the oxidative cleavage of 9,10-DSA is a material based on Au NPs deposited on Cp.

Determining kinetics of electrochemical carbon dioxide reduction to carbon monoxide with scanning electrochemical microscopy

This study reports on determining kinetics of electrochemical reduction CO2 to CO on Au catalysts using the substrate generation/tip collection (SG/TC) mode of scanning electrochemical microscopy (SECM). We introduced a simple but effective method based on transient technique to obtain a series of apparent heterogeneous rate constants k based on Fick’s second law by controlling the tip-substrate distance and the voltage of the substrate electrode within the SECM framework. By analysis the transient current recorded during the chronoamperometric characterization, we can successfully determine the apparent rate constant k for the simplified total conversion process of CO2 + 2H+ + 2e- → CO + H2O onto Au catalyst electrode serving as an example, which increases from 5.02 × 10–2 cm⋅s−1 to 7.16 × 10–2 cm⋅s−1 in the low potential range of −2.2 to −2.6 V (vs. Pt/PPy) and decreases to 6.54 × 10-2 cm⋅s−1 at –2.8 V (vs. Pt/PPy). The method proposed here can be applied to quantitatively analyze the kinetic of CO2 electrochemical reduction reaction, and thus provide a useful tool to guide the synthesis of catalyst as well as in-situ performance evaluation.

Electrochemical Redox Conversion of Formate to CO via Coupling Fe-Co Layered Double Hydroxides and Au Catalysts.

Formate has been considered an inactive molecule and thus cannot be further reduced under CO2 reduction conditions, which limits its widespread application as feedstock. Here we present an electrochemical redox conversion of formate to CO through the potential-dependent generation of carbon dioxide radical anions (CO2 ⋅- ) on Fe-Co layered double hydroxides (Fe-Co LDHs) and the subsequent reduction of CO2 ⋅- to CO on Au catalysts. We present an electrodeposition protocol for the synthesis of Fe-Co LDHs with precise composition control and find that Fe1 Co4 exhibits a promising potential window for CO2 ⋅- formation between 1.14 and 1.4 V and an optimized potential at 1.24 V at a neutral pH condition. We further determined the formation of CO2 ⋅- at 1.24 V via electron paramagnetic resonance and CO2 at >1.4 V through differential electrochemical mass spectrometry. This work provides a redox chemistry route for converting formate into CO through a coupled slit parallel-plate electrode system.

Oxidation of glycerol to dihydroxyacetone over highly stable Au catalysts supported on mineral-derived CuO-ZnO mixed oxide

Selective oxidation of glycerol to dihydroxyacetone (DHA) is a promising pathway for glycerol utilization. In order to fabricate a highly stable supported Au catalyst for the reaction, a series of CuO-ZnO mixed oxides derived from different minerals were synthesized. Then, the Au/CuO-ZnO catalysts were prepared by the deposition-precipitation. High yield of DHA (70%) and conversion of glycerol (76%) were obtained over the rosasite-derived Au/CuO-ZnO catalyst. While over the aurichalcite-derived Au/CuO-ZnO catalyst, the yield of DHA was only 20%. By means of XRD, H2-TPR, TEM, XPS, CO2-TPD characterization, it was found that the higher yield of DHA was attributed to the stronger interaction between CuO and ZnO, higher dispersion of Au species, higher content of Au0 and proper amount of surface basic sites. The rosasite-derived Au/CuO-ZnO catalyst also showed good stability and no obvious decrease in reactivity and DHA selectivity could be seen after five recycles. The stable structure of the support not only enhanced the interaction between CuO-ZnO that stabilized the support itself, but also improved the interaction between Au and the support, further stabilizing the particle size and chemical valence of Au.

Advanced quasi-2D amorphous TiOx-Au photocatalyst: Harnessing defects and carriers transport to boost visible-light organic pollutants degradation

Amorphous materials have recently garnered significant interest due to their low-cost fabrication methods, extensive surface area and plentiful surface defects, which offer numerous active sites for catalytic reactions. However, carriers self-trapping and recombination caused by bulk defects limit the employment of amorphous materials as photocatalysts. As such, it is essential to adjust the structure and defects to improve carriers utilization for creating high-performance amorphous photocatalysts. In this study, we developed a novel and facile strategy to fabricate a quasi-2D amorphous crepe-like TiOx-Au (cTiOx-Au) photocatalyst, in which the cTiOx was synthesized simply through one-step hydrolysis method at room temperature by constructing discrete reaction system with mass-confinement of the precursor to guide the morphology of the cTiOx. The removal efficiencies of the cTiOx-Au to antibiotic tetracycline (TC) and gaseous pollutant formaldehyde (HCHO) under visible light were 84.43 % and 95.92 %, respectively, which greatly surpassed those of its counterparts, normal amorphous TiOx (amTiOx)-Au (54.32 % and 73.67 %) and crystalline catalyst TiO2-P25-Au (49.29 % and 54.03 %). The remarkable visible-light photocatalytic capacity of cTiOx-Au can be attributed to the unique quasi-2D morphology of cTiOx. The ultrathin nanostructure not only maximizes surface defects and minimizes bulk defects, but also effectively shortens the carriers transport time and reduces recombination probability, on the other hand, it provides ample adsorption sites and accessible binding sites for plasmonic Au nanoparticles to amplify the effect of surface plasmon resonance enhancement. The excellent photocatalytic performances of cTiOx-Au for removing both aqueous and atmospheric pollutants endow it great potential in real environmental remediation applications.

Exploring catalytic oxidation pathways of furfural and 5-hydroxymethyl furfural into carboxylic acids using Au, Pt, and Pd catalysts: a comprehensive review

This review explores the mechanisms and factors influencing the selective oxidation of HMF and furfural into valuable products using gold, platinum, and palladium catalysts.

Understanding the growth mechanisms of γ-GeSe for polymorph-selective large-area deposition

This work unveils the pivotal roles of Au catalysts and substrates in the polymorph-selective, large-area synthesis of γ-GeSe. The demonstrated synthesis of γ-GeSe will advance energy storage and optoelectronics applications with the new polymorph.

Functionalisation of alkali-resistant nanoporous glass via Au nanoparticle decoration using alkaline impregnation: catalytic activity for CO removal.

The concerted use of nano-metal particles with catalytic functions and nanoporous materials holds promise for effective air purification and gas sensing; however, only a few studies have used porous glasses as supports for Au nanoparticles. Furthermore, Au/nanoporous glasses with activities comparable to that of Au/TiO2, which is a typical Au catalyst, have not been reported to date. This study demonstrates that a nanoporous glass, which is highly acid- and alkali-resistant and chemically stable, can be decorated with Au nanoparticles using an alkali impregnation method. The resulting composite exhibits high catalytic activity in CO oxidation. The catalysts reported herein are as active as Au/TiO2 catalysts per active site. Further optimisation of the pore properties of the glass and sizes of the Au nanoparticles is expected to result in excellent catalytic systems for CO removal and sensing.

Carbon-supported Au25 cluster catalysts partially decorated with dendron thiolates: enhanced loading weight and durability for hydrogen evolution reaction.

In order to establish a design principle for efficient Au electrocatalysis, it is desirable to synthesize a highly loaded, robust, and atomically precise Au cluster catalyst on a conductive carbon support. In this work, heterogeneous Au25 catalysts were prepared by calcining 5.0 wt% of mixed ligated [Au25(D2S)x(PET)18-x]0 (D2S = second generation Fréchet-type dendron thiolate, PET = 2-phenylethanethiolate) on a carbon support. X-ray absorption fine structure analysis, powder X-ray diffraction, and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) revealed the successful synthesis of carbon-supported partially thiolated Au25 clusters by calcining [Au25(D2S)10.7(PET)7.3]0 at 425 °C for ≥12 h, whereas calcination of [Au25(PET)18]0 under the same conditions resulted in thermally induced aggregation into larger Au nanoparticles. The D2S-modified Au25 catalyst showed better durability than PET-modified Au25 in electrocatalytic hydrogen evolution reaction. The higher durability was attributed to the suppression of aggregation of Au25 clusters during the reaction, as confirmed by AC-HAADF-STEM. These results indicate that the residual D2S ligands on Au25 enhance the stability against aggregation more than the residual PET due to stronger non-covalent interactions with carbon supports and/or greater steric hindrance of dendritic structure. This work demonstrates that the stability of Au catalysts can be improved by partial decoration with designed ligands.

Uncalcined TS-1 supported Au catalyst via NaBH4 reduction method for propylene epoxidation: Insights into the H2 pretreatment effect on catalytic performance

Stable and efficient Au-supported titanium silicalite-1 (TS-1) catalysts are essential for the direct epoxidation of propylene (DEP) using O2 and H2. But the deposition-precipitation method for Au/TS-1 contains low Au capture efficiency and rapid deactivation rate. Herein, Au/TS-1-B (uncalcined TS-1) catalysts were synthesized through a NaBH4 reduction method. The impact of H2-thermal-pretreatment on DEP activities was studied. H2-pretreatment can enhance propylene oxide selectivity, shorten activation time and reduce deactivation rate of catalyst. Organic-templates on the surface of TS-1-B and stabilizers coated on Au-nanoparticles can be partially removed under H2-treatment, thus exposing more active sites for Au and Ti and facilitating their interactions. Furthermore, more porous structures with reduced acid sites and enhanced surface hydrophobicity of pretreated catalyst can promote DEP reaction. Solid stability in TS-1-B, high Au utilization resulting from the reduction method, and favorable modifications through H2-thermal treatment contribute to the exploration of more robust DEP catalyst performance.

Au-decorated Sb2Se3 photocathodes for solar-driven CO2 reduction.

Photoelectrodes with FTO/Au/Sb2Se3/TiO2/Au architecture were studied in photoelectrochemical CO2 reduction reaction (PEC CO2RR). The preparation is based on a simple spin coating technique, where nanorod-like structures were obtained for Sb2Se3, as confirmed by SEM images. A thin conformal layer of TiO2 was coated on the Sb2Se3 nanorods via ALD, which acted as both an electron transfer layer and a protective coating. Au nanoparticles were deposited as co-catalysts via photo-assisted electrodeposition at different applied potentials to control their growth and morphology. The use of such architectures has not been explored in CO2RR yet. The photoelectrochemical performance for CO2RR was investigated with different Au catalyst loadings. A photocurrent density of ∼7.5 mA cm-2 at -0.57 V vs. RHE for syngas generation was achieved, with an average Faradaic efficiency of 25 ± 6% for CO and 63 ± 12% for H2. The presented results point toward the use of Sb2Se3-based photoelectrodes in solar CO2 conversion applications.

A hierarchically porous carbon stabilized atomically dispersed Au catalyst for acetylene hydrochlorination

The activity of the Au-CSC catalyst is significantly enhanced by the hierarchically porous structure derived from cationic starch, in comparison with that of the microporous Au-SC catalyst obtained from pristine starch.

Deconvoluting the Role of Electrolyte pH, Structural Sensitivity, and Electric Field Effects on the Electrochemical Hydrogenation of Phenol

Traditional thermochemical hydrogenation (TCH) methods that are used in the U.S. chemical and petroleum industries to produce value-added fuels are highly energy intensive. To achieve hydrogenation, they require high temperature and pressure, along with an external source of hydrogen that usually comes from steam methane reformation. Electrochemical hydrogenation (ECH) is an attractive alternative that replaces the thermal driving force with an applied electrical potential, allowing ECH to operate near ambient conditions. The participating protons come from the aqueous electrolyte solution rather than externally produced hydrogen. These features of ECH lower its energy demand compared to TCH and result in less greenhouse gas emissions. ECH is also promising for the processing of biomass feedstocks and could be powered directly by renewable energy, further minimizing the environmental impact.The addition of an aqueous electrolyte and electric field means that insights from TCH should not be directly translated to ECH systems, however, this is often the case in the literature. Fundamental studies on ECH of aromatic hydrocarbons (AHs) are necessary to address current limitations including: competition with the hydrogen evolution reaction (HER) resulting in lower faradaic efficiency, low rates compared to TCH, and little control over selectivity and degree of hydrogenation. For instance, the role of electrolyte pH on phenol ECH remains poorly understood. While some groups have reported negligible phenol turnover rates in electrolytes of pH 10 and above on Pt/C and Pd/C catalysts [1], Song et al. have shown that turnover rates and efficiency are highest on Rh/C at pH 10 [2]. Yet, the idea that low pH (3-5) is best has persisted and the source of the pH dependence remains unknown.In this work we use phenol as a simple representative AH for lignocellulosic bio-oil. We have shown with rotating disk electrode voltammetry that the presence of phenol in electrolytes of pH ~10 enhances HER rates on Pt, Pd, and Au catalysts. Considering that the pKa of phenol is also 10.0, we propose that interfacial phenol molecules channel protons to the catalyst surface by way of facile proton dissociation/reassociation, lowering the barrier for adsorbed H formation in alkaline electrolytes. While this may explain, in part, the low phenol turnover rates observed at higher pH, we further investigate why the opposite is observed on Rh/C catalysts. The role of atomic surface structure is also critical to the adsorption geometry and coverage of AHs. We use well-defined, low-index Pt single crystals to identify the true structural sensitivity for the ECH of AHs. We show with select stepped single crystal surfaces that there is a synergetic role between terrace width/step density that defines activity, balancing coverage of AH molecules, formation of surface adsorbed H, and transfer of that H to AH reactants. We use a low-volume, membrane-separated flow cell for chrono-amperometry followed by product analysis to correlate pH, structural sensitivity, and applied potential to phenol ECH rates and faradaic efficiency. With an understanding of the role of atomic surface structure and the true source of pH dependence, we propose strategies for enhancing phenol turnover rates at lower overpotentials, improving faradaic efficiency, and controlling selectivity.

Electrolyte Engineering for Improved Selectivity of Electrochemical CO2 Reduction

Electrochemical CO2 reduction reaction (eCO2RR) offers a promising solution to produce valuable chemical building blocks especially when coupled with renewable energy sources. However, its practical application faces significant challenges including low production selectivity due to competing hydrogen evolution reactions (HER). As both reactions are highly sensitive to the chemical environment formulated around active sites within electrochemical double layer (EDL), a comprehensive understanding is required on the role of electrolyte components, such as cation, anion, local pH, and water molecules, in tailoring chemical environment and thereby determining selectivity between eCO2RR and HER kinetics on the same catalyst surface.In this context, recent studies have shown that electrolyte engineering can largely control eCO2RR/HER selectivity.[2,3] For instance, different alkali cations have been shown to largely determine CO2 conversion kinetics due to their different hydrated structure within EDL structures.[4] Moreover, an increased cation population within EDL can promote effective eCO2RR over HER even under highly acidic conditions through charge screening effect.[5] Nevertheless, a lack of dynamic information from conventional experimental approaches (e.g. gas chromatography-mass spectrometry) is largely limiting our efforts to comprehensively understand electrolyte engineering effects. To advance our knowledge in electrolyte engineering for high eCO2RR selectivity, it is essential to investigate the functional correlation between electrolyte properties and eCO2RR/HER competition occurring at the electrochemical interface in operando manner.[6,7] In this work, we utilized in situ Differential Electrochemical Mass Spectrometry (DEMS) to monitor the effects of various electrolyte engineering on eCO2RR/HER selectivity in a dynamic manner. Based on the online collection of product molecules and CO2 from Au catalyst surface, in situ DEMS can provide detailed information on both reaction competition between eCO2RR and HER and local CO2 concentration on catalyst surface on electrified catalyst surface. Based on the strength of in situ DEMS analysis, the critical role of electrolyte components will be addressed in terms of eCO2RR/HER kinetics and the local chemical environment. Overall, this work will highlight importance of understanding specific role of electrolyte engineering toward designing efficient eCO2RR systems for carbon-neutral energy technology.[1] A. Wagner, C. D. Sahm, and E. Reisner, Nat. Catal. 2020, 3, 775–786.[2] J. C. Bui, C. Kim, A. J. King, O. Romiluyi, A. Kusoglu, A. Z. Weber, and A. T. Bell, Acc. Chem. Res. 2022, 55, 484-494.[3] G. Marcandalli, M. C. O. Monteiro, A. Goyal, and M. T. M. Koper, Acc. Chem. Res. 2022, 55,1900-1911.[4] M. C. O. Monteiro, F. Dattila, B. Hagedoorn, R. Garcia-Muelas, N. Lopez, and M. T. M. Koper, Nat. Catal. 2021, 4, 654-662.[5] J. Gu, S. Liu, W. Ni, W. Ren, S. Haussener, and X. Hu, Nat. Catal. 2022, 5, 268-276.[6] A. Goyal, G. Marcandalli, V. A. Mints, and M. T. M. Koper, J. Am. Chem. Soc. 2020, 142, 4154-4161[7] E. L. Clark and A. T. Bell, J. Am. Chem. Soc. 2018, 140, 7012-7020.

Oxygen vacancy-regulated atomic dispersed Au on CeFeOx for preferential oxidation of CO in H2-rich stream

CO preferential oxidation in H2-rich stream (CO-PROX) is a critical reaction for H2 purification in emerging hydrogen economy including advanced fuel cell technology. Au-based catalysts are viewed as some of the most promising catalysts but achieving high catalytic efficiency and selectivity is still challenging. Defect engineering is deemed as a powerful strategy to improve the intrinsic catalytic activity. Herein, CeFeOx-supported Au catalysts with controllable oxygen vacancy (Ov) concentrations were obtained and applied to CO-PROX. The results of characterizations showed that the Ovs were preferentially generated in conjunction with Au single atoms (SAs) rather than nanoparticles (NPs), which further modulated the surface electronic properties via surplus electrons in Ovs and enhanced the interfical interaction between Ovs and Au SAs. The CO-PROX results indicated that the reduced Au SA catalyst (Au1/CeFeOx-R) with the highest Ov concentration completely converted CO at temperature of 80 °C with relatively low reactivity towards H2 oxidation. The remarkable catalytic activity and selectivity were attributed to the modified electronic properties by Ovs that played a bridging role in electron transfer and accelerated reaction process, as well as the coupling effect of Ovs and Au SAs that enhanced the dissociative adsorption of O2 and the adsorption-oxidation of CO, resulting in a reduced reaction energy barrier and making CO oxidation more favorable than H2 oxidation. This research opens up an alternative strategy to simultaneously stabilize and activate single-atom catalysts.

Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols.

A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.