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Partial oxidation

About: Partial oxidation is a(n) research topic. Over the lifetime, 8261 publication(s) have been published within this topic receiving 205069 citation(s).


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Journal ArticleDOI
Abstract: The adsorption properties and reactivities of gold are summarized in terms of their size dependency from bulk to fine particles, clusters and atoms. The catalytic performances of gold markedly depend on dispersion, supports, and preparation methods. When gold is deposited on select metal oxides as hemispherical ultra-fine particles with diameters smaller than 5 run, it exhibits surprisingly high activities and/or selectivities in the combustion of CO and saturated hydrocarbons, the oxidation-decomposition of amines and organic halogenated compounds, the partial oxidation of hydrocarbons, the hydrogenation of carbon oxides, unsaturated carbonyl compounds, alkynes and alkadienes, and the reduction of nitrogen oxides. The unique catalytic nature of supported gold can be explained by assuming that the gold-metal oxide perimeter interface acts as a site for activating at least one of the reactants, for example, oxygen. Some examples and future prospects in applications are also briefly described.

3,743 citations

Journal ArticleDOI
07 Jan 2016-Nature
Abstract: Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially 'clean' strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2(•-) radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO(-)) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems, especially once the influence of both the atomic-scale structure and the presence of oxide are mechanistically better understood.

1,087 citations

Journal ArticleDOI
Abstract: Gold has long been thought to be chemically inert, however, it has recently been proven that its catalytic performance is dramatically tunable by control of the particle size and by careful selection of the support metal oxide. A typical example is the selective oxidation of propylene in a gas containing oxygen and hydrogen. When gold is deposited on TiO2by a deposition–precipitation technique as hemispherical particles with diameters smaller than 4.0 nm it produces propylene oxide with selectivities higher than 90% and conversions of 1–2% at temperatures of 303–393 K. The oxidation of hydrogen to form water is depressed by propylene, whereas propylene oxidation is not only enhanced but also restricted to partial oxidation by hydrogen. The depression of hydrogen combustion by the presence of propylene and a new peak due to gold deposition in TPD spectra have indicated that propylene is adsorbed on the surfaces of both gold particles and the TiO2support. The reaction rate is almost independent on the concentration of propylene and increases linearly with increasing concentrations of O2and H2. The above results suggest that propylene adsorbed on a gold surface may react with oxygen species formed at the perimeter interface between the gold particles and the TiO2support through the reaction of oxygen with hydrogen. The effect of gold loading is surprising in that the reaction product switches from propylene oxide to propane when gold loading is decreased to 0.1 wt%. Careful TEM observation indicates that gold particles larger than 2.0 nm in diameter produce propylene oxide, whereas smaller gold particles produce propane.

1,022 citations

Journal ArticleDOI
15 Jan 2010-Science
TL;DR: Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support that catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80°C.
Abstract: Gold (Au) is an interesting catalytic material because of its ability to catalyze reactions, such as partial oxidations, with high selectivities at low temperatures; but limitations arise from the low O2 dissociation probability on Au. This problem can be overcome by using Au nanoparticles supported on suitable oxides which, however, are prone to sintering. Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support. It catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80 degrees C. Because the overall catalytic characteristics of nanoporous Au are in agreement with studies on Au single crystals, we deduced that the selective surface chemistry of Au is unaltered but that O2 can be readily activated with this material. Residual silver is shown to regulate the availability of reactive oxygen.

917 citations

Journal ArticleDOI
20 Oct 2005-Nature
TL;DR: It is shown that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products and significant conversions.
Abstract: Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient. The introduction of catalytic systems using oxygen from air is preferred for 'green' processing. Gold catalysis is now showing potential in selective redox processes, particularly for alcohol oxidation and the direct synthesis of hydrogen peroxide. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide, hydroperoxides or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products ( approximately 98%) and significant conversions. Our finding significantly extends the discovery by Haruta that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.

891 citations

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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
202212
2021201
2020249
2019246
2018264
2017237