Base-free aerobic oxidation of glycerol on TiO2-supported bimetallic Au-Pt catalysts

(整期优先)网络出版时间:2015-05-15
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Theaerobicoxidationofglycerolprovidesaneconomicallyviableroutetoglyceraldehyde,dihydroxyacetoneandglycericacidwithversatileapplications,forwhichmonometallicPt,AuandPdandbimetallicAu–Pt,Au–PdandPt–PdcatalystsonTiO2wereexaminedunderbase-freeconditions.PtexhibitedasuperioractivityrelativetoPd,andAu–PdandPt–PdwhileAuwasessentiallyinactive.ThepresenceofAuontheAu–Pt/TiO2catalystsledtotheirhigheractivities(normalizedperPtatom)inawiderangeofAu/Ptatomicratios(i.e.1/3–7/1),andtheonewiththeAu/Ptratioof3/1exhibitedthehighestactivity.SuchpromotingeffectisascribedtotheincreasedelectrondensityonPtviatheelectrontransferfromAutoPt,ascharacterizedbythetemperature-programmeddesorptionofCOandinfra-redspectroscopyforCOadsorption.Meanwhile,thepresenceofAuonAu–Pt/TiO2,mostlikeduetotheobservedelectrontransfer,changedtheproductselectivity,andfacilitatedtheoxidationofthesecondaryhydroxylgroupsinglycerol,leadingtothefavorableformationofdihydroxyacetoneoverglyceraldehydeandglycericacidthatwerederivedfromtheoxidationoftheprimaryhydroxylgroups.ThesynergeticeffectbetweenAuandPtdemonstratesthefeasibilityintheefficientoxidationofglyceroltothetargetedproducts,forexample,byrationaltuningoftheelectronicpropertiesofmetalcatalysts.