Au Sites Research Articles

Photocatalytic Oxidative Coupling of Methane to Ethane Using CO2 as a Soft Oxidant over the Au/TiO2-Vo Nanosheets.

Photocatalytic oxidative coupling of methane (OCM) offers an appealing route for converting greenhouse gas into valuable C2 hydrocarbons. However, O2, as the most commonly used oxidant, tends to result in inevitable overoxidation and waste of methane feedstock. Herein, we first report a photocatalytic OCM using CO2 as a soft oxidant for C2H6 production under mild conditions, where an efficient photocatalyst with unique interface sites is designed and constructed to facilitate CO2 adsorption and activation, while concurrently boosting CH4 dissociation. As a prototype, the Au quantum dots anchored on oxygen-deficient TiO2 nanosheets are fabricated, where the Au-Vo-Ti interface sites for CO2 adsorption and activation are collectively disclosed by in situ Kelvin probe force microscopy, quasi in situ X-ray photoelectron spectroscopy and theoretical calculations. Compared with single metal site, the Au-Vo-Ti interface sites exhibit the lower CO2 adsorption energy and decrease the energy barrier of the *CO2 hydrogenation step from 1.05 to 0.77 eV via Au-C and Ti-O dual-site bonding. The adsorbed CO2 on the photocatalyst reduces the energy barrier of *CH4 dissociation to *CH3 from 2.13 to 1.59 eV, contributing to CH4 oxidation. Additionally, in situ Fourier-transform infrared spectroscopy unveils the Au site facilitates ethane production by engaging in *CH3-Au interaction and accelerating CH3-CH3 coupling. Thus, the photocatalyst demonstrates a high C2H6 evolution rate of 2.60 mmol g-1 h-1 for OCM using CO2 as the soft oxidant, surpassing most of previously reported photocatalysts regardless of OCM and nonoxidative coupling of methane. This work highlights the importance of soft oxidants for improving oxidation reaction efficiency and provides atomic scale insight into the design of photocatalysts for CH4 conversion.

Photocatalytic Oxidative Coupling of Methane to Ethane Using CO2 as a Soft Oxidant Over the Au/TiO2‐Vo Nanosheets

Herein, we first report a photocatalytic OCM using CO2 as a soft oxidant for C2H6 production under mild conditions, where an efficient photocatalyst with unique interface sites is constructed to facilitate CO2 adsorption and activation, while concurrently boosting CH4 dissociation. As a prototype, the Au quantum dots anchored on oxygen‐deficient TiO2 nanosheets are fabricated, where the Au‐Vo‐Ti interface sites for CO2 adsorption and activation are collectively disclosed by in situ Kelvin probe force microscopy, quasi in situ X‐ray photoelectron spectroscopy and theoretical calculations. Compared with single metal site, the Au‐Vo‐Ti interface sites exhibit the lower CO2 adsorption energy and decrease the energy barrier of the *CO2 hydrogenation step from 1.05 to 0.77 eV via Au‐C and Ti‐O dual‐site bonding. The adsorbed CO2 reduces the energy barrier of *CH4 dissociation to *CH3 from 2.13 to 1.59 eV, contributing to CH4 oxidation. Additionally, in situ Fourier‐transform infrared spectroscopy unveils the Au site facilitates ethane production by engaging in *CH3‐Au interaction and accelerating CH3‐CH3 coupling. Thus, the photocatalyst demonstrates a high C2H6 evolution rate of 2.60 mmol g‐1 h‐1 for OCM using CO2 as the soft oxidant, surpassing most of previously reported photocatalysts regardless of OCM and nonoxidative coupling of methane.

Constructing Heterojunction Photocatalyst Systems with Spatial Distribution of Au Single Atoms for CO2 Reduction.

In single-atomic photocatalyst systems, the spatial distribution of single atoms on heterojunctions and its impact on photocatalytic processes, particularly on carrier dynamics and the CO2 reduction process involving multielectron reactions, remains underexplored. To address this gap, a WO3/TiO2 nanotube heterojunction with a spatially selective distribution of Au single atoms was developed using an oxygen vacancy anchoring strategy for CO2 photoreduction. By anchoring Au atoms onto the WO3 or TiO2 components, a substantial number of active sites are generated and the electron transfer pathways from the heterojunction toward Au sites are formed, thereby enhancing carrier separation and concentration. As a result, the total yield of CO2 reduction products increases by 6.3 times and 3.9 times, respectively. More importantly, due to significant differences in adsorption properties, energy band structures, and reaction energy barrier, as well as a 2-fold difference in carrier lifetime, the selective distribution of Au single-atom sites results in completely different CO2 photoreduction products: when Au atoms are anchored on WO3 and TiO2 components, the product selectivity is 67.6% CH4 and 82.9% CO, respectively. This study clarifies the vital role of the spatial distribution of single atoms on the selectivity of electron-demanding products.

Satellite Pd Single-Atom Embraced AuPd Alloy Nanoclusters for Enhanced Hydrogen Evolution.

The fabrication of hybrid active sites that synergistically contain nanoclusters and single atoms (SAs) is vital for electrocatalysts to achieve excellent activity and durability. Herein, we develop a ligand-assisted pyrolysis strategy using nanoclusters (Au4Pd2(SC2H4Ph)8) with alloy cores and protected ligands to build AuPd cluster sites embraced by satellite Pd SAs. In the thermal drive control process, different thermodynamic properties of the alloy atoms and the confinement effects of organic ligands allow for the mild spillover of the single-component metal Pd, resulting in the formation of AuPd alloy nanoclusters tightly encompassed by isolated Pd atoms. Experiments and theoretical calculations indicated that the satellite Pd atoms can optimize the electronic structure of the AuPd nanoclusters and Au sites in the alloy to facilitate the adsorption and dissociation of H2O, thus enhancing the hydrogen evolution reaction (HER) activity. The optimal AuPdNCs/PdSAs-600 exhibits outstanding electrocatalytic activity toward HER, with overpotentials of 21 and 38 mV at 10 mA cm-2 in acidic and alkaline media, respectively. Moreover, the mass activity and turnover frequency of AuPdNCs/PdSAs-600 are one order of magnitude higher than those of commercial Pd/C and Pt/C catalysts. This facile strategy for constructing hybrid catalytic centers using ligand-protected nanoclusters provides efficient insights for the further design of nanocluster-based electrocatalysts synergized by SAs.

Selective electrooxidation of glucose towards gluconic acid on Ni@Au foam electrodes

Ni@Au electrodes are prepared by galvanic replacement of Ni atoms of a commercial Ni foam by Au atoms. The physicochemical characterizations indicate gold atomic ratios of ca. 6 %, independently on the galvanic replacement time (1, 2 and 3 min), but differences in the structure of the deposited gold layers. The shapes of the cyclic voltammograms recorded in a 0.1 M NaOH aqueous electrolyte indicate that both Au and Ni sites are accessible. In the presence of 0.1 M glucose, the same oxidation onset potential of ca. 0.3 V vs RHE and a comparable activity in terms of achieved geometric current densities were recorded for all the Ni@Au electrodes. The long term electrolyses of 0.1 M glucose in 0.1 M aqueous KOH electrolyte on the Ni@Au electrodes performed at cell voltages corresponding to anode potentials of 0.575 V, 0.675 V and 0.775 V vs RHE show a surprising excellent stability over 5 h, which is explained by the presence of a Ni(OH)2 layer on the surface of the Ni foam in contact with the deposited gold layers. Conversions up to 60 % are obtained after 5 h electrolyses with the Ni-Au electrode obtained after 3 min deposition, with 100 % selectivity and faradaic efficiency towards gluconic acid for all the electrodes and for the lower potential of 0.575 V vs RHE. Increasing the glucose and KOH initial concentrations decreases the conversion rate, selectivity and faradaic efficiency.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters

AbstractThe selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) selectively catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters.

The selective synthesis of valuable azo- and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine-tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF-8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) selectively catalyzed nitrobenzene reduction to azobenzene. X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO-DRIFTS) of Au NC/ZIF-8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF-8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF-8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure-selectivity relationships.

Modulating Ti coordination environment in Ti-containing materials by sulfation for synergizing with Au sites to facilitate propylene epoxidation

Modulating the coordination environment of Ti sites in Ti-containing materials to synergize with Au sites is a crucial issue to boost the process of propylene epoxidation with H2 and O2 to produce propylene oxide (i.e., HOPO), but still remains a great challenge. Herein, we report a facile strategy to tailor the coordination states and electronic properties of Ti sites. The sulfur-decorated Ti-SiO2 (i.e., Ti sites anchored onto silica) with moderate sulfur loading (Ti-SiO2-S-M) can synergize well with Au sites for the HOPO process with high activity, propylene oxide (PO) selectivity, and H2 efficiency, which are superior to those achieved on the referenced Ti-SiO2 synergizing with Au sites. Multiple characterizations, in-situ diffuse reflectance infrared Fourier transform spectroscopy of propylene and PO, PO conversion experiment, and kinetics behaviors demonstrate that the superior advantages of Ti-SiO2-S-M against Ti-SiO2 result from the increased Ti binding energy, improved hydrophobicity, and weakened acidity, which simultaneously facilitate the adsorption of propylene and promote the desorption of PO. This insight reported here could guide the rational design and optimization of Ti-containing materials to synergize with Au catalysts for propylene epoxidation.

Dynamic Control of Asymmetric Charge Distribution for Electrocatalytic Urea Synthesis.

Constructing dual catalytic sites with charge density differences is an efficient way to promote urea electrosynthesis from parallel and CO2 reduction yet still challenging in static system. Herein, a dynamic system is constructed by precisely controlling the asymmetric charge density distribution in an Au-doped coplanar Cu7 clusters-based 3D frameworkcatalyst (Au@cpCu7CF). In Au@cpCu7CF, the redistributed charge between Au and Cu atoms changed periodically with the application of pulse potentials switching between -0.2 and -0.6 V and greatly facilitated the electrosynthesis of urea. Compared with the static condition of pristine cpCu7CF (FEurea = 5.10%), the FEurea of Au@cpCu7CF under pulsed potentials is up to 55.53%. Theoretical calculations demonstrated that the high potential of -0.6V improved the adsorption of *HNO2 and *NH2 on Au atoms and inhibited the reaction pathways of by-products. While at the low potential of -0.2V, the charge distribution between Au and Cu atomic sites facilitated the thermodynamic C-N coupling step. This work demonstrated the important role of asymmetric charge distribution under dynamic regulation for urea electrosynthesis, providing a new inspiration for precise control of electrocatalysis.

Unveiling the mechanism of thorough electrocatalytic oxidation of monoethanolamine by ultramicroelectrode and fast-scan cyclic voltammetry

The electro-oxidation of monoethanolamine (MEA) is relevant from fundamental and applied, viz. sewage treatment, fuel cell and electrochemical water splitting, perspectives. Understanding mechanistic details of thorough electrocatalytic oxidation of MEA is of paramount importance for the rational design of high-performing electrocatalysts. Herein, in order to easily and quickly quantify the electro-oxidation degree of MEA and therefore assist the mechanism study, the present paper proposes an innovative strategy for determining the number of electrons transferred in the electro-oxidation of intermediates, with the aid of ultramicroelectrode (UME) and fast-scan cyclic voltammetry (CV). Deconvolutions on two fast-scan CV oxidation peaks, one of which is originated from the electro-oxidation of MEA to glycine intermediate and the other is the further electro-oxidation of intermediate, reveal that the number of electrons transferred in the electro-oxidation of glycine intermediates is merely 3.04±0.75 on pure Au catalyst, indicating the incomplete conversion of glycine to ammonia and glyoxylate ion. The introduction of trace Ni into Au electrocatalyst can remarkably boost the number of electrons transferred, an indication of more thorough electro-oxidation of glycine intermediates and thereby more bio-friendly degradation products. Theoretical calculations based on the density functional theory elucidate that such increase in electro-oxidation degree is due to the stronger adsorption of glycine intermediates on AuNi binary sites than on sole Au sites.

Laser-Generated Au nanoparticles as lithophilic sites in self-supported film host for anode-free lithium metal battery

Anode-free lithium metal batteries (AFLMBs) are considered to have greater application potential than traditional LMBs because of their higher energy density and safety. Unfortunately, their poor cycling performances originated from the unsatisfactory reversibility of Li plating/stripping remains a big challenge. A rational designed host for lithium deposition is an effective solving strategy. Herein, pure Au nanoparticles (NPs) without any impurities are prepared by a liquid-phase laser irradiation technology to construct and develop a self-supported Au/reduced graphene oxide (Au/rGO) film as lithium deposition host for AFLMBs. The densely and uniformly distributed Au NPs provide abundant lithiophilic sites that significantly reduce the nucleation barrier of lithium. Attributed to the precise regulation of Au sites towards lithium nucleation/growth, dendrites-free anode and improved electrochemical performance are obtained by using the Au/rGO film host. It keeps stable for 30 min of lithiation at 6 mA cm−2 without dendrite formation. Additionally, the Li||Au/rGO half-cell shows an overpotential close to 0 mV and maintains a Coulombic efficiency exceeding 97 % after 500 cycles at 1 mA cm−2. Moreover, a symmetric Au/rGO-Li cell can operate for 700 h without short-circuit. When paired with LiFePO4 (LFP) to assemble a full battery, the Au/rGO-Li achieves 96 % capacity retention rate after 100 cycles. This work not only develops an efficient host for lithium, but also provides a unique strategy to the safety concerns associated with LMBs’ anodes.

Interfacial Engineering of Mn Porphyrin/Au Electrodes for Identifying MnOx as the Active Species under Oxygen Evolution Reactions.

Understanding the influence of surface structural features at a molecular level is beneficial in guiding an electrode's mechanistic proposals for electrocatalytic reactions. The relationship between structural stability and catalytic activity significantly impacts reaction performance, even though atomistic knowledge of active sites remains a topic of discussion. In this context, this work presents scanning tunneling microscopy (STM) results for the highly ordered arrangement of manganese porphyrin molecules on a Au(111) surface; STM allows us to monitor active sites at a molecular level to focus on long-standing issues with the electrocatalytic process, especially the exact nature of the real active sites at the interfaces. After water oxidation, manganese porphyrin rapidly decomposes into active catalytic species as bright protrusions. These newly formed active species drastically lost catalytic activity, up to 82%, through only acid treatment, one of the oxide removal methods, not by deionized water and acetone treatments. STM results of the obviated active species on the Au surface by an acidic solution support the forfeited catalytic activity. In addition, it shows a 67% decrement in catalytic activity by adsorption of phosphonic acid, one of the oxide's preferred adsorption materials, compared to the pristine one. Based on these observations, we confirm that the newly formed active species, as water oxidation catalysts, mostly consist of manganese oxides. Notable findings of our work provide molecular evidence for the active sites of Au and modified Au electrodes that spur the future development of water oxidation catalysts.

Photoactive Porphyrin-Based Covalent Organic Frameworks for Photocatalytic Applications

The incorporation of porphyrin units into covalent organic frameworks (COFs) brings new photoelectrochemical properties to the resulted systems. We have developed a bottom-up strategy to prepare a series of tailor-made chiral COFs. The porphyrin subunits act as antennae to harvest visible light. Meanwhile, various secondary amine-based chiral functional groups are immobilized on the pore walls of COFs as catalytic sites. As a result, the COFs that are elaborately designed to merge photoactive building blocks and chiral catalytic sites achieve high production yields with good enantiomeric excess in photocatalytic asymmetric alkylation of aldehydes. In further studies, we have also prepared isostructural porphyrin-based COFs with high crystallinity and porosity, and investigated their photocatalytic N2 fixation performance. The porphyrin building blocks act as not only light-harvesting antennae, but also docking sites for anchoring Au single atoms. Moreover, the microenvironment of Au sites and optoelectronic properties of photocatalysts could be finely tuned by designing the functional groups on proximal and distal position of porphyrin units. The structure-activity relationship has been studied in detail by combining experimental results and theoretical calculations. The introduction of electron-withdrawing groups facilitates the separation and transportation of photogenerated electrons within the entire framework, thus promoting the adsorption of N2 on Au sites for achieving high performance of N2 conversion into NH3.

Insights into the Structure and Activity of Bimetallic Au/Cu2O Catalysts during CO2 Electroreduction to C2 products

Despite its promising performance for C2+ product formation in electrochemical reduction of CO2 (CO2RR), Cu-based catalysts exhibit a relatively poor selectivity towards important chemical intermediates such as ethylene and ethanol. Up to 16 different products can typically be formed during CO2RR.1 Cu is the only element that can form C-C bonds at an appreciable rate.2 Therefore, it is critical to better understand the active sites of Cu-based electrocatalysts, as it can lead to better catalyst design with improved selectivity towards desired products. A common approach is to investigate the reactivity of well-defined surface terminations of Cu, which can be achieved by employing shape-controlled (nano)particles.3 Here, we expanded on such studies by evaluating the impact of Au on well-defined Cu2O surfaces for the electrochemical reduction of CO2. This promoter metal was chosen, because it can reduce CO2 to CO, which is widely accepted as the key intermediate for C-C coupling.2,4 In this study, 40 nm Cu2O nanocubes that predominantly expose the (100) facet were synthesized with a ligand-free method. The (100) facet is more active in the production of ethylene at the expense of unwanted methane formation, which takes place predominantly at the (111) facet.3 The surface of the nanocubes was decorated with Au nanoparticles by a galvanic replacement reaction. HAADF-STEM images of the catalysts with various Au loadings are shown in Figure 1a-d. After addition of Au nanoparticles, the shape of the Cu2O nanocubes was preserved. However, the Au nanoparticles were highly dispersed at low loadings (1 mol % Au) whereas Au clusters were observed at higher loadings (10 mol % Au). This result was in line with synchrotron X-ray diffraction (XRD) results, whereby the Au(111) reflection appears for the 10Au/Cu2O sample. Besides, the formation of a Au-Cu alloy and CuO phase was confirmed as well. The highly dispersed nature of the Au nanoparticles at low loadings was further established by Au 4f X-ray photoelectron spectroscopy (XPS), whereby a shift towards higher binding energies was observed as compared to the samples with higher Au loadings. The electrocatalytic performance of the catalysts was assessed over a range of potentials in neutral electrolyte (0.1 M KHCO3) in H-cell configuration. With highly dispersed Au as promotor, we found that the formation of ethylene and ethanol was significantly enhanced (Figure 1e-f). More specifically, the Faradaic effiency towards ethanol increased by roughly 1.5 times by introducing 1 mol % Au to the Cu2O nanocubes. Surprisingly, the 10Au/Cu2O sample displayed the lowest Faradaic efficiency for C2 products. We believe that the dispersion of Au on the Cu2O surface plays an important role in the product formation, whereby CO can be formed at Au sites and diffuse to Cu sites in proximity for further reduction to C2 products (CO spillover). To further study structure-activity relationships, we performed in-situ X-ray absorption spectroscopy (XAS) measurements. Figure 1g shows the normalized Cu K-edge X-ray absorption near-edge structure (XANES) of the Cu2O and Au/Cu2O samples in the final state. The evolution of the Cu(0), Cu(I) and Cu(II) fractions was followed by Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) analysis. This analysis revealed that the final oxidation state of the catalysts is different. The Cu(I)/Cu(0) ratio shows the following trend 1Au/Cu2O > 5Au/Cu2O > Cu2O > 10Au/Cu2O. Based on these observations, we hypothesize that the oxidation state of Cu affects the product distribution and in particular, the formation of oxygenates. The presence of Cu(I) species and the formation of Cu(0) species during CO2 electroreduction was further confirmed with in-situ XRD measurements. Finally, we performed quasi in-situ XPS measurements to study the reduction of the surface of the catalysts. Acknowledgements This publication is part of the research programme 'Reversible Large-scale Energy Storage' (RELEASE) with project number 17621 which is financed by the Dutch Research Council (NWO).

Mechanistic Aspects of Selenate Reduction on CU(UPD) on AU Electrodes

Recent findings in our laboratories have shown that copper1and cadmium2 underpotential deposited on polycrystalline Au electrodes, can mediate the reduction of in 0.1 M HClO4 aqueous solutions, to yield irreversibly adsorbed elemental Se allowing its detection down to the nM range. Current efforts are focused on gaining a better understanding of the the factors that govern this unique electrocatalytic phenomenon by employing a combination of electrochemical, microgravimetric, and optical techniques, using Cu as the UPD species. Correlations have been sought between the rates of this process and the coverage of Cu(UPD), the concentration of and, to a more limited extent, the applied potential in 0.1 M HClO4 solutions. Experimental conditions were selected to unveil the functional dependence of the kinetics on each of the aforementioned factors, while keeping the others constant, in solutions both quiescent and in the presence of convective flow. A number of interesting observations were made based on the data collected. In particular, shown in Panel C, Fig. 1, are plots of the charge associated with the oxidation of adsorbed Cu and Se, QCu and QSe, respectively (see Panel C), obtained from the area under the peaks shaded in light blue and yellow in Panels A and B, Fig, 1, respectively, vs (see below). These data were recorded during linear potential scans following polarization of the electrode at Ehold = 0.325 V for various times, thold (see Panels A-C, Fig. 1), where the linear character of the data in solutions is consistent with Cu(UPD) proceeding under strict diffusion control. As indicated by the QSe data, the electrode displayed electrocatalytic activity for reduction only for QCu > ca. 80 μC cm2-. Additional insight was obtained from measurements of the electrode weight as a function of using a quartz crystal microbalance (see Panel D, Fig.1), which yielded evidence for adsorption only for QCu > ca. 80 μC cm2-, pointing to the formation of a surface-bound adduct, as a necessary step for reduction to ensue. On this basis, we propose that for QCu > ca. 80 μC cm2 the mechanism for reduction involves, as a first step, the reversible formation of the adduct, Eq. (1) followed by its irreversible reduction, generating adsorbed elemental Se, Cu|Se(ads), Eq. (2).Atomically resolved images of Cu(UPD) on Au(111) obtained with a scanning tunneling microscope for the closely related sulfate ion, strongly suggest that the active site involved adsorption on the empty Au sites of the so-called √3´x√3 superstructure (see Insert in Panel A, Fig. 1). A similar conclusion was drawn based on measurements performed with rotating Cu ring-polycrystalline Au disk electrodes, RRDE, at constant Cu(UPD) coverage and applied potential for various solution compositions. Quantitative analyses of all the data, which included numerical simulations, yielded kf/kr, and kET values in the range (2.4 – 3.23) ´ 106 cm3 mol-1 and (2.5 – 9) ´ 10-3 s-1, respectively. Acknowledgments Support for this work was provided by NSF CHEM 1808592

Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation

Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation

Regulating interaction with surface ligands on Au25 nanoclusters by multivariate metal–organic framework hosts for boosting catalysis

ABSTRACT While atomically precise metal nanoclusters (NCs) with unique structures and reactivity are very promising in catalysis, the spatial resistance caused by the surface ligands and structural instability poses significant challenges. In this work, Au25(Cys)18 NCs are encapsulated in multivariate metal–organic frameworks (MOFs) to afford Au25@M-MOF-74 (M = Zn, Ni, Co, Mg). By the MOF confinement, the Au25 NCs showcase highly enhanced activity and stability in the intramolecular cascade reaction of 2-nitrobenzonitrile. Notably, the interaction between the metal nodes in M-MOF-74 and Au25(Cys)18 is able to suppress the free vibration of the surface ligands on the Au25 NCs and thereby improve the accessibility of Au sites; meanwhile, the stronger interactions lead to higher electron density and core expansion within Au25(Cys)18. As a result, the activity exhibits the trend of Au25@Ni-MOF-74 > Au25@Co-MOF-74 > Au25@Zn-MOF-74 > Au25@Mg-MOF-74, highlighting the crucial roles of microenvironment modulation around the Au25 NCs by interaction between the surface ligands and MOF hosts.

Revisiting the electrochemical reduction of CO2 on Au25(SR)18− nanocluster

Experiments show that Au25(SR)18− is a potential electrocatalyst for the electrochemical reduction of CO2, but elucidation of the reaction mechanisms remain challenging experimentally. We evaluate key steps in the active site formation, CO2 reduction, and H2 evolution on the nanocluster employing density functional theory coupled with an explicit solvent model of the electrochemical interface to calculate activation barriers. The predicted preferred pathway for activating the nanocluster involves dethiolation, resulting in an exposed Au site that is both active and selective for CO2 reduction. The alternative S site is found to be kinetically prohibitive and does not facilitate CO2 reduction.

Understanding electron structure of covalent triazine framework embraced with gold nanoparticles for nitrogen reduction to ammonia

Regulating the electron structure and precise loading sites of metal-active sites within the highly conjugated and porous covalent-triazine frameworks (CTFs) is essential to promoting the nitrogen reduction reaction (NRR) performance for electrocatalytic ammonia (NH3) synthesis under ambient conditions. Herein, experimental method and density functional theory (DFT) calculations were conducted to deeply probe the effect on NRR of the modulation of modulating the electron structure and the loading site of gold nanoparticles (Au NPs) in a two-dimensional (2D) CTF. 2D CTF synthesized using melem and hexaketocyclohexane octahydrate as building blocks (denoted as M−HCO−CTF) served as a robust scaffold for loading Au NPs to form an M−HCO−CTF@AuNP hybrid. DFT results uncovered that well-defined Au sites with tunable local structure were the active site for driving the NRR, which can significantly suppress the conversion of H+ into *H adsorption and enhance the nitrogen (N2) adsorption/activation. The overlapped Au (3d) and *N2 (2p) orbitals lowered the free energy of the rate-determining step to form *NNH, thereby accelerating the NRR. The M−HCO−CTF@AuNPs electrocatalyst exhibited a large NH3 yield rate of 66.3 μg h−1 mg−1cat. and a high Faraday efficiency of 31.4 % at − 0.2 V versus reversible hydrogen electrode in 0.1 M HCl, superior to most reported CTF-based ones. This work can provide deep insights into the modulation of the electron structure of metal atoms within a porous organic framework for artificial NH3 synthesis through NRR.

UV activated formaldehyde gas sensing based on gold decorated ZnO@ In2O3 hollow nanospheres at room temperature

Using uniform carbon nanospheres as sacrificial templates, gold nanoparticle-modified ZnO@ In2O3 hollow nanospheres with controlled dimensions and porous architectures were successfully synthesized through water bath, hydrothermal and chemical reduction methods. Gas sensing evaluation revealed that the Au-decorated ZnO@ In2O3 hollow nanostructures exhibited a dramatically amplified response up to 14.8 when exposed to 10 ppm formaldehyde analyte at room temperature. Furthermore, multifaceted performance benefits of Au-decorated ZnO@ In2O3 over single-phase ZnO, Au-ZnO, ZnO@ In2O3 heterojunction-based composites were observed, including excellent selectivity towards formaldehyde even in complex gas mixtures; tremendous sensitivity enhancement stemming from synergies between efficient gas diffusion through hollow heterojunction nanospheres and accelerated surface reactions at catalytically-active Au sites; and rapid, fully-reversible response/recovery time of 32 s and 42 s, respectively. In-depth investigations were conducted into the fundamental sensing mechanisms enabling formaldehyde detection using AC impedance spectroscopy, in situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), and density functional theory (DFT) computational modeling analyses.