The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in ele...The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.展开更多
Decays resulting from infections by Geotrichum citri-aurantii cause a significant reduction in citrus postharvest quality and marketable yield.In the present work,0.8 mol·L^(-1)NaCl of Generally Recognized as Saf...Decays resulting from infections by Geotrichum citri-aurantii cause a significant reduction in citrus postharvest quality and marketable yield.In the present work,0.8 mol·L^(-1)NaCl of Generally Recognized as Safe(GRAS)salts were identified to have complete inhibition activity to G.citriaurantii in vitro and in vivo.An inhibitory mechanism study showed that 0.1 mol·L^(-1)NaCl changed the expression of six genes(Gci002087,Gci003354,Gci000013,Gci000394,Gci003505 and Gci004433)in target of rapamycin(TOR)pathway,thus inducing a large number of lipid droplets(LDs)accumulation with TEM observations and staining.In vivo,0.1 mol·L^(-1)NaCl could raise up the activities of CAT,PAL,PPO and cellulase which hence to strengthen the ability of resistance tolerance of citrus.In addition,NaCl not only accelerated the growth of the biocontrol yeast Kloeckera apiculata strain 34-9,but also increased the expression level of adhesin-encoding genes and biofilm-formation encoding gene(34-9-3691).Finally,the storage experiments in 3 months demonstrated that the combination of NaCl and the yeast 34-9 could keep fresh,reduce decay and prolong its shelf-life,thus implying that the combination of biocontrol strain and GRAS salts has been explored as a promising alternative to synthetic fungicides.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087)the Postdoctoral Research Foundation of China(Grant No.2022M721360)the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。
文摘The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.
基金supported by the National Natural Science Foundation of China(Grant Nos.32302170&32172255)HZAU-AGIS Cooperation Fund(Grant No.SZYJY2023001)。
文摘Decays resulting from infections by Geotrichum citri-aurantii cause a significant reduction in citrus postharvest quality and marketable yield.In the present work,0.8 mol·L^(-1)NaCl of Generally Recognized as Safe(GRAS)salts were identified to have complete inhibition activity to G.citriaurantii in vitro and in vivo.An inhibitory mechanism study showed that 0.1 mol·L^(-1)NaCl changed the expression of six genes(Gci002087,Gci003354,Gci000013,Gci000394,Gci003505 and Gci004433)in target of rapamycin(TOR)pathway,thus inducing a large number of lipid droplets(LDs)accumulation with TEM observations and staining.In vivo,0.1 mol·L^(-1)NaCl could raise up the activities of CAT,PAL,PPO and cellulase which hence to strengthen the ability of resistance tolerance of citrus.In addition,NaCl not only accelerated the growth of the biocontrol yeast Kloeckera apiculata strain 34-9,but also increased the expression level of adhesin-encoding genes and biofilm-formation encoding gene(34-9-3691).Finally,the storage experiments in 3 months demonstrated that the combination of NaCl and the yeast 34-9 could keep fresh,reduce decay and prolong its shelf-life,thus implying that the combination of biocontrol strain and GRAS salts has been explored as a promising alternative to synthetic fungicides.
