Strong metal‐support interaction boosting the catalytic activity of Au/TiO_(2) in chemoselective hydrogenation

Gold catalysts have been reported as highly effective catalysts in various oxidation reactions.However,for chemoselective hydrogenation reactions,gold‐based catalysts normally show much lowercatalytic activity than platinum group metals,even though their selectivities are excellent.Here,wereport that the chemoselective hydrogenation activity of 3‐nitrostyrene to 3‐vinylaniline overAu/TiO_(2)can be enhanced up to 3.3 times through the hydrogen reduction strategy.It is revealedthat strong metal‐support interaction,between gold nanoparticles(NPs)and TiO_(2)support,is introducedthrough hydrogen reduction,resulting in partial dispersion of reduced TiOx on the Au surface.The partially covered Au not only increases the perimeter of the interface between the gold NPs andthe support,but also benefits H_(2)activation.Reaction kinetic analysis and H_(2)‐D2 exchange reactionshow that H_(2)activation is the critical step in the hydrogenation of 3‐nitrostyrene to 3‐vinylaniline.Density functional theory calculations verify that hydrogen dissociation and hydrogen transfer arefavored at the interface of gold NPs and TiO_(2)over the hydrogen‐reduced Au/TiO_(2).This study providesinsights for fabricating highly active gold‐based catalysts for chemoselective hydrogenationreactions.

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel:Preparation and application as plasticizer

Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

Selective and stable Au-Cu bimetallic catalyst for CO-PROX

Gold-based catalysts are promising in CO preferential oxidation(CO-PROX)reaction in H_(2)-rich stream on account of their high intrinsic activity for CO elimination even at ambient temperature.However,the decrease of CO conversion at elevated temperature due to the competition of H_(2)oxidation,together with the low stability of gold nanoparticles,has posed a dear challenge.Herein,we report that Au-Cu bimetallic catalyst prepared by galvanic replacement method shows a wide temperature window for CO total conversion(30-100℃)and very good catalyst stability without deactivation in a 200-h test.Detailed characterizations combined with density functional theory(DFT)calculation reveal that the synergistic effect of Au-Cu,the electron transfer from Au to Cu,leads to not only strengthened chemisorption of CO but also weakened dissociation of H_(2),both of which are helpful in inhibiting the competition of H_(2)oxidation thus widening the temperature window for CO total conversion.

Disruption of a microvitellogenin gene impairs eggshell formation in Mythimna separata

Microvitellogenin(mVg)belongs to the lepidopteran-specific lipoprotein_11 super family and is thought to be involved in insect reproduction.However,the function of mVg in reproduction has not been established.In this study,we identified and characterized MsmVg in Mythimna separata,a destructive insect pest of grain crops.MsmVg is comprised of a 1,310 bp open reading frame(ORF)encoding 437 amino acids.Structural analysis showed that MsmVg contains three conserved domains in the lipoprotein_11 super family,including the all-α-N-terminal domain(NTD),a Pseudomonas putida homologous domain(PPD),and an all-β-C-terminal domain(CTD).MsmVg was highly expressed in mature female adults and enriched in the ovaries of 3-day-old female adults.Disruption of MsmVg by RNA interference did not change the expression of MsmVg,vitellogenin(MsVg)or the vitellogenin receptor(MsVgR)in fat bodies,but it inhibited their transcription in ovaries.Phenotype analysis showed that knockdown of MsmVg did not affect yolk deposition in ovaries,but impaired eggshell formation and led to a reduction in the reproductive capacity.Furthermore,knockdown of MsmVg significantly inhibited the expression of genes associated with eggshell formation(MsChP1-3 and MsFcP3C).Taken together,these data suggest that MsmVg plays an important role in female reproduction by affecting eggshell formation in M.separata,which provides a potential target for managing this insect pest.