The transformation of CO2 into alcohols or other hydrocarbon compounds is challenging because the difficulties associated with chemical activation by heterogeneous catalysts. Pure metals and bimetallic systems used for this task usually have low catalytic activity. Here we present experimental theoretical evidence a completely different type site activation: copper-ceria interface that highly efficient synthesis methanol. combination metal oxide sites in affords complementary properties lead...

Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y z = 1, x:y:z 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content Ni, Co, Mn significantly affects both structural changes oxygen release features during heating: more Ni less Co Mn, lower onset temperature...

The electronic properties of Pt nanoparticles deposited on CeO(2)(111) and CeO(x)/TiO(2)(110) model catalysts have been examined using valence photoemission experiments density functional theory (DFT) calculations. DFT results point to a new type "strong metal-support interaction" that produces large perturbations for small particles in contact with ceria significantly enhances the ability admetal dissociate O-H bonds water. When going from Pt(111) Pt(8)/CeO(2)(111), dissociation water...

The high thermochemical stability of CO2 makes it very difficult to achieve the catalytic conversion molecule into alcohols or other hydrocarbon compounds, which can be used as fuels starting point for generation fine chemicals. Pure metals and bimetallic systems → CH3OH usually bind too weakly and, thus, show low activity. Here, we discuss a series recent studies that illustrate advantages metal–oxide metal–carbide interfaces when aiming at methanol. CeOx/Cu(111), Cu/CeOx/TiO2(110),...

Metallic silver (Ag) is known as an efficient electrocatalyst for the conversion of carbon dioxide (CO2) to monoxide (CO) in aqueous or nonaqueous electrolytes. However, polycrystalline electrocatalysts require significant overpotentials order achieve high selectivity toward CO2 reduction, compared side reaction hydrogen evolution. Here we report a high-surface-area Ag nanocoral catalyst, fabricated by oxidation–reduction method presence chloride anions medium, electro-reduction CO with...

Abstract Ni‐CeO 2 is a highly efficient, stable and non‐expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the consists small nanoparticles nickel dispersed on partially reduced ceria. Experiments ambient pressure XPS indicate that dissociates Ni/CeO as 300 K, generating CH x CO species surface catalyst. Strong metal–support interactions activate Ni dissociation methane. results density‐functional calculations show drop in effective barrier...

Where oxide and metals meet: The activation of an efficient associative mechanistic pathway for the water–gas shift reaction by oxide–metal interface leads to increase in catalytic activity nanoparticles ceria deposited on Cu(111) or Au(111) more than order magnitude (see graph). In situ experiments demonstrated that a carboxy species formed at metal–oxide is critical intermediate reaction. As service our authors readers, this journal provides supporting information supplied authors. Such...

CeO takes charge: Ceria grows forming small islands on terraces (2–5 nm, CeOx-I) and large steps of a copper substrate (30–50 CeOx-II; see scheme; 100×100 nm2). The resulting CeOx/Cu(111) systems display an extraordinary water-gas shift activity illustrate the role that oxide can play in improving performance copper-based catalysts. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They...

A water boost for methanol synthesis Model catalysts based on metals and metal oxides can dissociate methane (CH 4 ) at room temperature, converting it directly to 3 OH). Liu et al. show that one of these catalysts, an “inverted” CeO x -Cu 2 O oxide Cu(111), tunes the selectivity from forming CO surface CH groups, as revealed by ambient-pressure x-ray photoelectron spectroscopy. Theoretical modeling showed adsorbed blocks dissociation instead oxidizes reduced catalyst. Hydroxyl groups...

The steam reforming of ethanol on a Ni-based CeO2-supported catalyst was studied using in situ X-ray diffraction (XRD), operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and mass (MS) with focus the structural characterization catalysts, chemical identification reaction pathway, understanding interaction between Ni CeO2 support. Ethoxy, acetate, carbonate, hydroxyl species are identified by DRIFTS as surface intermediates that appear during process. oxidation...

Water dissociation is crucial in many catalytic reactions on oxide-supported transition-metal catalysts. Supported by experimental and density-functional theory results, the effect of support OH bond cleavage activity elucidated for nickel/ceria systems. Ambient-pressure O 1s photoemission spectra at low Ni loadings CeO2 (111) reveal a substantially larger amount OH groups as compared to bare support. Computed activation energy barriers water show an enhanced reactivity adatoms with...

Capture and recycling of CO2 into valuable chemicals such as alcohols could help mitigate its emissions the atmosphere. Due to inert nature, activation is a critical step in improving overall reaction kinetics during chemical conversion. Although pure gold an noble metal cannot catalyze hydrogenation reactions, it can be activated when deposited nanoparticles on appropriate oxide support. In this combined experimental theoretical study, shown that electronic polarization at metal-oxide...

Oxides play a central role in important industrial processes, includingapplications such as the production of renewable energy, remediation environmental pollutants, and synthesis fine chemicals. They were originally used catalyst supports thought to be chemically inert, but now they are build catalysts tailored toward improved selectivity activity chemical reactions. Many studies have compared morphological, electronic, properties oxide materials with those unoxidized metals. Researchers...

CO2 hydrogenation to methanol has attracted increasing attention with the development of renewable hydrogen. A big challenge is identify catalysts able achieve high conversion and selectivity. Here, we report an In2O3-supported Au catalyst that exhibits excellent performance for selectively methanol. In situ characterizations using time-resolved X-ray diffraction, ambient-pressure photoelectron spectroscopy, absorption spectroscopy confirm a strong metal–support interaction leads reactive...

Metal–organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge rationally design construct MOFs that can serve as highly stable reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) (Ni), been prepared by modulated synthetic strategy. The are assembled...

Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study adsorption and decomposition simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, NU-1000 using synchrotron-based X-ray powder diffraction, absorption, infrared spectroscopy, which reveals key aspects reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at...

The metal–oxide interaction changes the surface electronic states of catalysts deployed for chemical conversion, yet details its influence on catalytic performance under reaction conditions remain obscure. In this work, we report high activity/stability a ceria-supported Ru–nanocluster (<1 nm) catalyst during dry reforming methane. To elucidate structure–reactivity relationship underlying remarkable performance, active structure and speciation was characterized using in situ X-ray...

The role of the interface between a metal and oxide (CeOx–Cu ZnO–Cu) is critical to production methanol through hydrogenation CO2 (CO2 + 3H2 → CH3OH H2O). deposition nanoparticles CeOx or ZnO on Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts for synthesis. catalytic activity these systems increases in sequence: Cu(111) ZnO/Cu(111) CeOx/Cu(111). apparent activation energy conversion decreases from 25 kcal/mol 16 13 surface chemistry CeOx–Cu(111) was investigated using ambient...

The results of core-level photoemission indicate that Ni-CeO2(111) surfaces with small or medium coverages nickel are able to activate methane at 300 K, producing adsorbed CHx and COx (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy 0.6–0.7 eV for the cleavage first C–H bond in molecule. Ni O centers ceria work cooperative way dissociation room temperature, where loading is crucial catalyst activity stability. strong electronic...

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is great environmental interest remains a challenge despite many efforts. Extended surfaces metallic nickel are inactive for direct CH4 → CH3OH conversion. This experimental computational study provides clear evidence that low Ni loadings on CeO2(111) support can perform catalytic cycle the generation using oxygen water as reactants, with selectivity than ever reported ceria-based...

A combination of time-resolved X-ray diffraction (TR-XRD), ambient-pressure photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform was used to carry out in situ characterization Cu/CeO2 nanocatalysts during the hydrogenation CO2. Morphological effects ceria supports on catalytic performances were investigated by examining behavior copper/ceria nanorods (NR) nanospheres. At atmospheric pressures, CO2 catalysts produced mainly CO through reverse water–gas shift...

Abstract Oxide-supported noble metal catalysts have been extensively studied for decades the water gas shift (WGS) reaction, a catalytic transformation central to host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as how specific features active metal-support interfacial bonding—perhaps most importantly temporal dynamic changes occurring therein—serve enable high activity and selectivity. Here we report characteristics Pt/CeO 2...

The methane activation and dry reforming reactions were studied compared over 4 wt % Ni/CeO2 Ni/CeZrO2 (containing 20 Zr) catalysts. Upon the incorporation of Zr into ceria support, catalyst exhibited a significantly improved activity H2 selectivity. To understand effects dopant on Ni CeO2 during (DRM) reaction to probe structure–reactivity relationship underlying enhanced catalytic performance mixed-oxide system, in situ time-resolved X-ray diffraction (TR-XRD), absorption fine structure...