Carbon and sulphur on Pd(111) and Pt(111): Experimental problems during cleaning of the substrates and impact of sulphur on the redox properties of CeOx in the CeOx/Pd(111) system

The X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and CO titration has been used to detect common impurities like carbon and sulphur on Pd(111) and Pt(111) surfaces. Different experimental problems are discussed and practical tips for the cleaning of Pd(111) and Pt(111) are given. A mechanism for the carbon oxidation on closed packed platinum group metals like Pt(111) and Pd(111) is presented. The bulk carbon concentration of Pd(111) was estimated based on the Langmuir-McLean theorem. Additionally it was shown that the titration with CO and subsequent XPS measurement is a powerful yet convenient method for quantitative detection of impurities and ceria coverage determination. A CeO_x/Pd(111) inverse model system was prepared by evaporation of cerium in an oxygen atmosphere. The comparative study has shown that sulphur contamination changes the redox properties of the CeO_x in the CeO_x/Pd(111) system.     

Gold catalysts for the abatement of environmentally harmful materials: Modeling the structure dependency

FeO_x, TiO₂ and CeO_x layers were deposited by pulsed laser deposition (PLD) technique onto Au films or Au nanoparticles supported on SiO₂/Si(100). The samples were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS) and their reactivity was studied in catalytic CO oxidation. Comparison was made with reference samples of FeO_x/SiO₂/Si(100), TiO₂/SiO₂/Si(100), CeO_x/SiO₂/Si(100) and Au/SiO₂/Si(100) layers. The catalytic activity of the metal-oxide/Au/SiO₂/Si(100) samples must be attributed to active sites located on the metal-oxides overlayer modified by gold underneath, since no Au was exposed to the surface according to the XPS and SIMS. We found a promoting effect of gold on the catalytic activity of the FeO_x overlayer and an inhibiting effect of gold on the TiO₂ and CeO_x overlayers. These findings are discussed in terms of electronic interactions at the Au/metal oxide interface.     

Atomic Layers of MoO2 with Exposed High‐Energy (010) Facets for Efficient Oxygen Reduction

Although 2D nanocrystals with exposed high‐energy facets are highly desired in the field of catalysts due to their anticipant high catalytic activities, they are difficult to be gained. Here, atomic layers of metallic molybdenum dioxide (MoO₂) with primarily exposed high‐energy (010) facet are achieved via a facile carbothermic reduction approach. The resultant MoO₂ exhibits single‐crystalline, monoclinic, and ultrathin features with nearly 100% exposed (010) facet, which can significantly reduce reaction barriers toward the oxygen reduction reaction. As a consequence, the atomic layers of MoO₂ exhibit high electrocatalytic activity, excellent tolerance to methanol, and good stability for the oxygen reduction reaction in alkaline electrolyte, superior to commercial Pt/C catalysts. It is believed that such new transition metal oxide catalysts with exposed high‐energy facets have broad applications in the areas of energy storage and conversions.     

Ultrafast Laser Manufacture of Stable,Efficient Ultrafine Noble Metal Catalysts Mediated with MOF Derived High Density Defective Metal Oxides

Supported metal nanoparticles (MNPs) undergo severe aggregation, especially when the interaction between MNPs and their supports are limited and weak where their performance deteriorates dramatically. This becomes more severe when catalysts are operated under high temperature. Here, it is reported that MNPs including Pt, Au, Rh, and Ru, with sub‐2 nm size can be stabilized on densely packed defective CeO₂ nanoparticles with sub‐5 nm size via strong coupling by direct laser conversion of corresponding metal ions encapsulated cerous metal–organic frameworks (Ce‐MOFs). Ce‐MOF serves as an ideal dispersion precursor to uniformly encapsulate noble metal ions in their orderly arranged pores. Ultrafast laser vaporization and cooling forms uniform, ultrasmall, well‐mixed, and exceptionally dense nanoparticles of metal and metal oxide concurrently. The laser‐induced ultrafast reaction (within tens of nanoseconds) facilitates the precipitation of CeO₂ nanoparticles with abundant surficial defects. Due to the well‐mixed ultrasmall Pt and CeO₂ components with strong coupling, this catalyst exhibits exceptionally high stability and activity both at low and high temperatures (170–1100 °C) for CO oxidation in long‐term operation, significantly exceeding catalysts prepared by traditional methods. The scalable feature of laser and huge MOF family make it a versatile method for the production of MNP‐based nanocomposites in wide applications.     

Ceria Nanocrystals Exposing Wide (100) Facets: Structure and Polarity Compensation

Compact CeO₂(111) films grown on Ru(0001) can be transformed into well‐shaped nanoparticles by annealing them in an oxygen‐poor environment. With increasing temperature, the particles undergo a distinct shape evolution that finally leads to crystallites exposing wide (100) facets. The atomic structure of the (100) termination is determined with a combination of high‐resolution scanning tunneling microscopy and density functional theory. Two surface reconstructions are identified that are compatible with the need to compensate for the intrinsic dipole of the (100) plane and with a substantial reduction of the oxide material. Our study provides insights into the rarely explored (100) surface of ceria, which can be considered as model system for studying chemical processes on the polar termination of reducible oxides.     

Catalytic properties of Pt cluster-decorated CeO2 nanostructures

Uniform clusters of Pt have been deposited on the surface of capping-agent-free CeO₂ nanooctahedra and nanorods using electron beam (e-beam) evaporation. The coverage of the Pt nanocluster layer can be controlled by adjusting the e-beam evaporation time. The resulting e-beam evaporated Pt nanocluster layers on the CeO₂ surfaces have a clean surface and clean interface between Pt and CeO₂. Different growth behaviors of Pt on the two types of CeO₂ nanocrystals were observed, with epitaxial growth of Pt on CeO₂ nanooctahedra and random growth of Pt on CeO₂ nanorods. The structures of the Pt clusters on the two different types of CeO₂ nanocrystals have been studied and compared by using them as catalysts for model reactions. The results of hydrogenation reactions clearly showed the clean and similar chemical surface of the Pt clusters in both catalysts. The support-dependent activity of these catalysts was demonstrated by CO oxidation. The Pt/CeO₂ nanorods showed much higher activity compared with Pt/CeO₂ nanooctahedra because of the higher concentration of oxygen vacancies in the CeO₂ nanorods. The structure-dependent selectivity of dehydrogenation reactions indicates that the structures of the Pt on CeO₂ nanorods and nanooctahedra are different. Thes differences arise because the metal deposition behaviors are modulated by the strong metal-metal oxide interactions.     

Abundant Ce3+ Ions in Au‐CeOx Nanosheets to Enhance CO2 Electroreduction Performance

The electroreduction of CO₂ to CO provides a potential way to solve the environmental problems caused by excess fossil fuel utilization. Loading transition metals on metal oxides is an efficient strategy for CO₂ electroreduction as well as for reducing metal usage. However, it needs a great potential to overcome the energy barrier to increase CO selectivity. This paper describes how 8.7 wt% gold nanoparticles (NPs) loaded on CeO_x nanosheets (NSs) with high Ce³⁺ concentration effectively decrease the overpotential for CO₂ electroreduction. The 3.6 nm gold NPs on CeO_x NSs containing 47.3% Ce³⁺ achieve CO faradaic efficiency of 90.1% at ?0.5 V in 0.1 m KHCO₃ solution. Furthermore, the CO₂ electroreduction activity shows a strong relationship with the fractions of Ce³⁺ on Au‐CeO_x NSs, which has never been reported. In situ surface‐enhanced infrared absorption spectroscopy shows that Au‐CeO_x NSs with high Ce³⁺ concentration promote CO₂ activation and *COOH formation. Theoretical calculations also indicate that the improved performance is attributed to the enhanced *COOH formation on Au‐CeO_x NSs with high Ce³⁺ fraction.     

Large‐Pore Mesoporous CeO2–ZrO2 Solid Solutions with In‐Pore Confined Pt Nanoparticles for Enhanced CO Oxidation

Active and stable catalysts are highly desired for converting harmful substances (e.g., CO, NO_x) in exhaust gases of vehicles into safe gases at low exhaust temperatures. Here, a solvent evaporation–induced co‐assembly process is employed to design ordered mesoporous Ce_xZr_1?xO₂ (0 ≤ x ≤ 1) solid solutions by using high‐molecular‐weight poly(ethylene oxide)‐block‐polystyrene as the template. The obtained mesoporous Ce_xZr_1?xO₂ possesses high surface area (60–100 m² g^?1) and large pore size (12–15 nm), enabling its great capacity in stably immobilizing Pt nanoparticles (4.0 nm) without blocking pore channels. The obtained mesoporous Pt/Ce_0.8Zr_0.2O₂ catalyst exhibits superior CO oxidation activity with a very low T₁₀₀ value of 130 °C (temperature of 100% CO conversion) and excellent stability due to the rich lattice oxygen vacancies in the Ce_0.8Zr_0.2O₂ framework. The simulated catalytic evaluations of CO oxidation combined with various characterizations reveal that the intrinsic high surface oxygen mobility and well‐interconnected pore structure of the mesoporous Pt/Ce_0.8Zr_0.2O₂ catalyst are responsible for the remarkable catalytic efficiency. Additionally, compared with mesoporous Pt/Ce_xZr_1?xO₂‐s with small pore size (3.8 nm), ordered mesoporous Pt/Ce_xZr_1?xO₂ not only facilitates the mass diffusion of reactants and products, but also provides abundant anchoring sites for Pt nanoparticles and numerous exposed catalytically active interfaces for efficient heterogeneous catalysis.     

Direct Experimental Observation of Facet‐Dependent SERS of Cu2O Polyhedra

Semiconductor‐based surface enhanced Raman scattering (SERS) has attracted great attention due to its excellent spectral reproducibility, high uniformity, and good anti‐interference ability. However, its relatively low SERS sensitivity still hinders its further developments in both performance and applications. Since the SERS is a peculiar surface effect, investigating the facet‐dependent SERS activity of semiconductor nanostructures is crucial to boost their SERS signals. Although the semiconductor facet‐dependent SERS effect is predicted via numerical calculations, convincing experimental evidence is scarce due to complicated and undefined surface conditions. In this work, three facet‐defined ({100}, {110}, and {111} facets) Cu₂O microcrystals (MCs) with clear surface atomic configuration are utilized to investigate the facet‐dependent SERS effect. The results from the Kelvin probe force microscopy measurements on single Cu₂O polyhedron, demonstrate that the facet‐dependent work function plays a crucial role in the interfacial charge transfer process. Comparing with the {110} and {111} facets, the {100} facet possesses the lowest electronic work function, which enables more efficient interfacial charge transfer. The simulation results further confirm that the {100}‐facets can transfer the most electrons from Cu₂O MCs to molecules due to its lowest facet work function, resulting in the largest increment of the molecular polarization.     

Growth, structure and electronic properties of ultrathin cerium oxide films grown on Pt(111)

Ultrathin cerium oxide films have been prepared by oxidizing Ce-Pt/Pt(111) surface alloys with 65 L O₂ at 900 K. According to low electron energy diffraction data, phonon spectra recorded by high resolution electron energy loss spectroscopy and scanning tunneling microscopy measurements the films are of fluorite-type CeO₂(111) structure. They grow three dimensionally as islands, which are flat and up to several hundred square nanometers large. The film thickness varies between one and five layers. The band gap of the oxide films has been probed by scanning tunneling spectroscopy and turned out to be significantly smaller than for bulk CeO_2.     

Low‐Energy Facets on CdS Allomorph Junctions with Optimal Phase Ratio to Boost Charge Directional Transfer for Photocatalytic H2 Fuel Evolution

Low‐energy facets on CdS allomorph junctions with optimal phase ratio are designed to boost charge directional transfer for photocatalytic H₂ fuel evolution. Fermi energy level difference between low‐energy facets as driving force promotes electrons directional transfer to hexagonal CdS(102) facet and holes to cubic CdS(111) facet. The optimal allomorphs CdS presents superior photocatalytic H₂ evolution rate of 32.95 mmol g^?1 h^?1 with release in a large amount of visible H₂ bubbles, which is much higher than single‐phase CdS with high‐energy facets and even supports noble metal photocatalysts. This scientific perspective on low‐energy facets of allomorph junctions with optimal phase ratio breaks the long‐held view of pursuing high‐energy crystal surfaces, which will break the understanding on surface structure crystal facet engineering of photocatalytic materials.     

A General and Straightforward Route to Noble Metal‐Decorated Mesoporous Transition‐Metal Oxides with Enhanced Gas Sensing Performance

Controllable and efficient synthesis of noble metal/transition‐metal oxide (TMO) composites with tailored nanostructures and precise components is essential for their application. Herein, a general mercaptosilane‐assisted one‐pot coassembly approach is developed to synthesize ordered mesoporous TMOs with agglomerated‐free noble metal nanoparticles, including Au/WO₃, Au/TiO₂, Au/NbO_x, and Pt/WO₃. 3‐mercaptopropyl trimethoxysilane is applied as a bridge agent to cohydrolyze with metal oxide precursors by alkoxysilane moieties and interact with the noble metal source (e.g., HAuCl₄ and H₂PtCl₄) by mercapto (? SH) groups, resulting in coassembly with poly(ethylene oxide)‐b‐polystyrene. The noble metal decorated TMO materials exhibit highly ordered mesoporous structure, large pore size (≈14–20 nm), high specific surface area (61–138 m² g^?1), and highly dispersed noble metal (e.g., Au and Pt) nanoparticles. In the system of Au/WO₃, in situ generated SiO₂ incorporation not only enhances their thermal stability but also induces the formation of ε‐phase WO₃ promoting gas sensing performance. Owning to its specific compositions and structure, the gas sensor based on Au/WO₃ materials possess enhanced ethanol sensing performance with a good response (R_air/R_gas = 36–50 ppm of ethanol), high selectivity, and excellent low‐concentration detection capability (down to 50 ppb) at low working temperature (200 °C).     

Electrocatalytic N‐Doped Graphitic Nanofiber – Metal/Metal Oxide Nanoparticle Composites

Carbon‐based nanocomposites have shown promising results in replacing commercial Pt/C as high‐performance, low cost, nonprecious metal‐based oxygen reduction reaction (ORR) catalysts. Developing unique nanostructures of active components (e.g., metal oxides) and carbon materials is essential for their application in next generation electrode materials for fuel cells and metal–air batteries. Herein, a general approach for the production of 1D porous nitrogen‐doped graphitic carbon fibers embedded with active ORR components, (M/MO_x, i.e., metal or metal oxide nanoparticles) using a facile two‐step electrospinning and annealing process is reported. Metal nanoparticles/nanoclusters nucleate within the polymer nanofibers and subsequently catalyze graphitization of the surrounding polymer matrix and following oxidation, create an interconnected graphite–metal oxide framework with large pore channels, considerable active sites, and high specific surface area. The metal/metal oxide@N‐doped graphitic carbon fibers, especially Co₃O₄, exhibit comparable ORR catalytic activity but superior stability and methanol tolerance versus Pt in alkaline solutions, which can be ascribed to the synergistic chemical coupling effects between Co₃O₄ and robust 1D porous structures composed of interconnected N‐doped graphitic nanocarbon rings. This finding provides a novel insight into the design of functional electrocatalysts using electrospun carbon nanomaterials for their application in energy storage and conversion fields.     

Micellar Nanoreactors Enabled Site-Selective Decoration of Pt Nanoparticles Functionalized Mesoporous SiO2/WO3-x Composites for Improved CO Sensing

Site-selective and partial decoration of supported metal nanoparticles (NPs) with transition metal oxides (e.g., FeO_x) can remarkably improve its catalytic performance and maintain the functions of the carrier. However, it is challenging to selectively deposit transition metal oxides on the metal NPs embedded in the mesopores of supporting matrix through conventional deposition method. Herein, a restricted in situ site-selective modification strategy utilizing poly(ethylene oxide)-block-polystyrene (PEO-b-PS) micellar nanoreactors is proposed to overcome such an obstacle. The PEO shell of PEO-b-PS micelles interacts with the hydrolyzed tungsten salts and silica precursors, while the hydrophobic organoplatinum complex and ferrocene are confined in the hydrophobic PS core. The thermal treatment leads to mesoporous SiO₂/WO_3-x framework, and meanwhile FeO_x nanolayers are in situ partially deposited on the supported Pt NPs due to the strong metal-support interaction between FeO_x and Pt. The selective modification of Pt NPs with FeO_x makes the Pt NPs present an electron-deficient state, which promotes the mobility of CO and activates the oxidation of CO. Therefore, mesoporous SiO₂/WO_3-x-FeO_x/Pt based gas sensors show a high sensitivity (31 ± 2 in 50 ppm of CO), excellent selectivity, and fast response time (3.6 s to 25 ppm) to CO gas at low operating temperature (66 °C, 74% relative humidity).     

Combination of supported bimetallic rhodium–molybdenum catalyst and cerium oxide for hydrogenation of amide

Abstract

Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6–7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh–MoO_x/SiO₂, and the addition of CeO₂ much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2–8 MPa and 393–433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh–MoO_x/SiO₂ + CeO₂ was 63%. The effect of CeO₂ addition was highest when CeO₂ was not calcined, and CeO₂ calcined at >773 K showed a smaller effect. The use of CeO₂ as a support rather decreased the activity in comparison with Rh–MoO_x/SiO₂. The weakly-basic nature of CeO₂ additive can affect the surface structure of Rh–MoO_x/SiO₂, i.e. reducing the ratio of Mo–OH/Mo–O^? sites.     

Amorphizing of Au Nanoparticles by CeOx–RGO Hybrid Support towards Highly Efficient Electrocatalyst for N2 Reduction under Ambient Conditions

Ammonia synthesis is one of the most kinetically complex and energetically challenging chemical processes in industry and has used the Harber–Bosch catalyst for over a century, which is processed under both harsh pressure (150–350 atm) and hightemperature (623–823 K), wherein the energy and capital intensive Harber–Bosch process has a huge energy cost accounting for about 1%–3% of human's energy consumption. Therefore, there has been a rough and vigorous exploration to find an environmentally benign alternative process. As the amorphous material is in a metastable state and has many “dangling bonds”, it is more active than the crystallized one. In this paper, CeO_x ‐induced amorphization of Au nanoparticles anchored on reduced graphite oxide (a‐Au/CeO_x –RGO) has been achieved by a facile coreduction method under ambient atmosphere. As a proof‐of‐concept experiment, a‐Au/CeO_x –RGO hybrid catalyst containing the low noble metal (Au loading is 1.31 wt%) achieves a high Faradaic efficiency (10.10%) and ammonia yield (8.3 μg h^?1 mg^?1_cat.) at ?0.2 V versus RHE, which is significantly higher than that of the crystalline counterpart (c‐Au/RGO), and even comparable to the yields and efficiencies under harsh temperatures and/or pressures.     

Promoted Glycerol Oxidation Reaction in an Interface‐Confined Hierarchically Structured Catalyst

Confined catalysis in a 2D system is of particular interest owing to the facet control of the catalysts and the anisotropic kinetics of reactants, which suppress side reactions and improve selectivity. Here, a 2D‐confined system consisting of intercalated Pt nanosheets within few‐layered graphene is demonstrated. The strong metal–substrate interaction between the Pt nanosheets and the graphene leads to the quasi‐2D growth of Pt with a unique (100)/(111)/(100) faceted structure, thus providing excellent catalytic activity and selectivity toward one‐carbon (C1) products for the glycerol oxidation reaction. A hierarchically porous graphene architecture, grown on carbon cloth, is used to fabricate the confined catalyst bed in order to enhance the mass‐diffusion limitation in interface‐confined reactions. Owing to its unique 3D porous structure, this graphene‐confined Pt catalyst exhibits an extraordinary mass activity of 2910 mA mg_Pt ^?1 together with a formate selectivity of 79% at 60 °C. This paves the way toward rational designs of heterogeneous catalysts for energy‐related applications.     

Engineering Bimetallic Ag–Cu Nanoalloys for Highly Efficient Oxygen Reduction Catalysts: A Guideline for Designing Ag‐Based Electrocatalysts with Activity Comparable to Pt/C‐20%

Development of highly active and stable Pt‐free oxygen reduction reaction catalysts from earth‐abundant elements remains a grand challenge for highly demanded metal–air batteries. Ag‐based alloys have many advantages over platinum group catalysts due to their low cost, high stability, and acceptable oxygen reduction reaction (ORR) performance in alkaline solutions. Nevertheless, compared to commercial Pt/C‐20%, their catalytic activity still cannot meet the demand of commercialization. In this study, a kind of catalysts screening strategy on Ag_x Cu_100?x nanoalloys is reported, containing the surface modification method, studies of activity enhancement mechanism, and applied research on zinc–air batteries. The results exhibit that the role of selective dealloying (DE) or galvanic displacement (GD) is limited by the “parting limitation”, and this “parting limitation” determines the surface topography, position of d‐band center, and ORR performance of Ag_x Cu_100?x alloys. The GD‐Ag₅₅Cu₄₅ and DE‐Ag₂₅Cu₇₅ catalysts alloys present excellent ORR performance that is comparable to Pt/C‐20%. The relationship between electronic perturbation and specific activity demonstrates that positive shift of the d‐band center (≈0.12 eV, relative to Ag) for GD‐Ag₅₅Cu₄₅ is beneficial for ORR, which is contrary to Pt‐based alloys (negative shift, ≈0.1 eV). Meanwhile, extensive electrochemical and electronic structure characterization indicates that the high work function of GD‐Ag₅₅Cu₄₅ (4.8 eV) is the reason behind their excellent durability for zinc–air batteries.     

Surface self-diffusion of adatom on Pt cluster with truncated octahedron structure

Surface diffusion of single Pt adatom on Pt cluster with truncated octahedron structure is investigated through a combination of molecular dynamics and nudged elastic band method. Using an embedded atom method to describe the atomic interactions, the minimum energy paths are determined and the energy barriers for adatom diffusion across and along step are evaluated. The diffusion of adatom crossing step edge between {111} and {100} facets has a surprisingly low barrier of 0.03 eV, which is 0.12 eV lower than the barrier for adatom diffusion from {111} to neighboring {111} facet. Owing to the small barrier of adatom diffusion across the step edge between {111} and {100} facets, the diffusion of adatom along the step edge cannot occur. The molecular dynamics simulations at low temperatures also support these results. Our results show that mass transport will prefer step with {100} microfacet and the Pt clusters can have only {111} facets in epitaxial growth.     

Promoting effect of CeO<Subscript>2</Subscript> on cyclohexanol conversion over CeO<Subscript>2</Subscript>-ZnO mixed oxide materials prepared by amorphous citrate process

CeO₂-ZnO materials were prepared by amorphous citrate process and characterized by TGA, XRD, UV-DRS and surface area measurements. TGA showed that the citrate precursors decompose in the range 350–550°C producing CeO₂-containing catalytic materials. XRD and DRS results indicated the formation of well-dispersed interstitialZn _xCe⁴⁺ _1−2x Ce³⁺ _2x O₂ solid solution on ZnO matrix. Addition of CeO₂ to ZnO produced high surface area mixed oxide materials in citrate method. Cyclohexanol conversion reaction was carried out on these catalytic materials to investigate the effect of rare earth oxide on the activity and selectivity. It was found that CeO₂ promotes the activity of ZnO without affecting the selectivity to cyclohexanone significantly. The factors such as reaction temperature and WHSV have turned out to be important for cyclohexanol conversion over CeO₂-containing ZnO catalyst materials.