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 p...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.展开更多
A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of ni...A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of nitroarenes with hydrazine monohydrate as a reductant under mild reaction conditions without pressure and base,which was different from other hydrogen transfer systems that require the presence of a base(e.g.,propan‐2‐ol/KOH).The sandwiching of carbon between the MoS2nanosheets increased the distance between the layers of MoS2and exposed more Mo sites,resulting in superior catalytic performance compared with that of bulk MoS2catalyst.The active hydrogen(H*)generated from N2H4could directly transfer to the–NO2groups of nitrobenzene to form aniline followed by N2emission,which was confirmed by detecting the gas emission with mass spectrometry during the decomposition of hydrazine or the co‐existence of nitrobenzene and hydrazine.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
In order to improve the yield and stability of ferrate in solution, dissolved Fe(Ⅵ) prepared with NaOH and KOH respectively was compared in this study. The results showed that KOH is more suitable than NaOH for the p...In order to improve the yield and stability of ferrate in solution, dissolved Fe(Ⅵ) prepared with NaOH and KOH respectively was compared in this study. The results showed that KOH is more suitable than NaOH for the preparation of dissolved Fe(Ⅵ) at temperature over 50 ℃. It is found that the dissolved Fe(Ⅵ) prepared with KOH increases quickly at first, and then slowly with the increasing concentrations of OH-and ClO-, while it increases rapidly at first and then decreases rapidly with the increasing dosage of Fe(NO3)3·9H2O. These results are different from that prepared with NaOH. It can be explained that solid K2FeO4 salts can be formed in KOH solution, and it will lower the Fe(Ⅵ) concentration, counteract the decomposition of Fe(Ⅵ), and improve the yield of Fe(Ⅵ). The maximum ferrate concentration is 0.163 mol/L obtained by 100 g/L Fe(NO3)3·9H2O and 6.16 mol/L KOH at 65 ℃. The stability of Fe(VI) is greatly improved due to the hypochlorite existed in the dissolved ferrate, and only 24% Fe(Ⅵ) has been decomposed after 16 d for 1 mmol/L Fe(Ⅵ) at 25 ℃.展开更多
The aim of our study was to better understand the different responses of rice seedling to different species of inorganic arsenic As203 (As(Ill)) and Na2HAsO4 (As(V)). Our results indicate that the biomass of r...The aim of our study was to better understand the different responses of rice seedling to different species of inorganic arsenic As203 (As(Ill)) and Na2HAsO4 (As(V)). Our results indicate that the biomass of rice seedling decreased as arsenic concentration increased, with the decrease being more significant at higher arsenic concentrations. In addition, the analysis of superoxide dimutase (SOD), peroxidase (POD), and catalase (CAT) in rice roots and leaves showed that the activity of these three enzymes significantly decreased in rice tissues, especially in rice roots, as arsenic concentration was increased,. Further, the uptake and utilization efficiencies of N, P, and K were found to decrease as arsenic concentration was increased. However, the uptake and utilization efficiencies of P and K were mainly affected by As(IlI), whereas those of N were mainly affected by As(V). Inductively coupled plasma-mass spectrometry (ICP-MS) was used to assay arsenic accumulation in rice tissues; the results indicate that the arsenic content in rice tissues was enhanced when arsenic concentration was increased, especially in rice roots after arsenic treatment.展开更多
When humic acid (HA) and phosphorus (P) fertilizer are simultaneously applied to soil, HA may affect the movement of P. A laboratory incubation experiment was conducted to quantify the effects of a commercial HA produ...When humic acid (HA) and phosphorus (P) fertilizer are simultaneously applied to soil, HA may affect the movement of P. A laboratory incubation experiment was conducted to quantify the effects of a commercial HA product co-applied with monocalcium phosphate (MCP) on the distance of P movement and the concentration of P in various forms at different distances from the P fertilizer application site in a calcareous soil from northern China. Fertilizer MCP (at a rate equivalent to 26.6 kg P ha-1 ) was applied alone or in combination with HA (at 254.8 kg HA ha-1 ) to the surface of soil packed in cylinders (150 mm high and 50 mm internal diameter), and then incubated at 320 g kg-1 moisture content for 7 and 28 d periods. Extraction and analysis of each 2 mm soil layer in columns showed that the addition of HA to MCP increased the distance of P movement and the concentrations of water-extractable P, acid-extractable P and Olsen P in soil. The addition of HA to MCP could enhance P availability by increasing the distance of P movement and the concentration of extractable P in soil surrounding the P fertilizer.展开更多
文摘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.
基金supported by the Ministry of Science and Technology(MOST,2016YFA0204100 and 2011CBA00504)the National Natural Science Foundation of China(21573254,91545110)+1 种基金the Youth Innovation Promotion Association(CAS)the Sinopec China~~
文摘A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of nitroarenes with hydrazine monohydrate as a reductant under mild reaction conditions without pressure and base,which was different from other hydrogen transfer systems that require the presence of a base(e.g.,propan‐2‐ol/KOH).The sandwiching of carbon between the MoS2nanosheets increased the distance between the layers of MoS2and exposed more Mo sites,resulting in superior catalytic performance compared with that of bulk MoS2catalyst.The active hydrogen(H*)generated from N2H4could directly transfer to the–NO2groups of nitrobenzene to form aniline followed by N2emission,which was confirmed by detecting the gas emission with mass spectrometry during the decomposition of hydrazine or the co‐existence of nitrobenzene and hydrazine.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘In order to improve the yield and stability of ferrate in solution, dissolved Fe(Ⅵ) prepared with NaOH and KOH respectively was compared in this study. The results showed that KOH is more suitable than NaOH for the preparation of dissolved Fe(Ⅵ) at temperature over 50 ℃. It is found that the dissolved Fe(Ⅵ) prepared with KOH increases quickly at first, and then slowly with the increasing concentrations of OH-and ClO-, while it increases rapidly at first and then decreases rapidly with the increasing dosage of Fe(NO3)3·9H2O. These results are different from that prepared with NaOH. It can be explained that solid K2FeO4 salts can be formed in KOH solution, and it will lower the Fe(Ⅵ) concentration, counteract the decomposition of Fe(Ⅵ), and improve the yield of Fe(Ⅵ). The maximum ferrate concentration is 0.163 mol/L obtained by 100 g/L Fe(NO3)3·9H2O and 6.16 mol/L KOH at 65 ℃. The stability of Fe(VI) is greatly improved due to the hypochlorite existed in the dissolved ferrate, and only 24% Fe(Ⅵ) has been decomposed after 16 d for 1 mmol/L Fe(Ⅵ) at 25 ℃.
文摘The aim of our study was to better understand the different responses of rice seedling to different species of inorganic arsenic As203 (As(Ill)) and Na2HAsO4 (As(V)). Our results indicate that the biomass of rice seedling decreased as arsenic concentration increased, with the decrease being more significant at higher arsenic concentrations. In addition, the analysis of superoxide dimutase (SOD), peroxidase (POD), and catalase (CAT) in rice roots and leaves showed that the activity of these three enzymes significantly decreased in rice tissues, especially in rice roots, as arsenic concentration was increased,. Further, the uptake and utilization efficiencies of N, P, and K were found to decrease as arsenic concentration was increased. However, the uptake and utilization efficiencies of P and K were mainly affected by As(IlI), whereas those of N were mainly affected by As(V). Inductively coupled plasma-mass spectrometry (ICP-MS) was used to assay arsenic accumulation in rice tissues; the results indicate that the arsenic content in rice tissues was enhanced when arsenic concentration was increased, especially in rice roots after arsenic treatment.
基金Supported by the Shandong Provincial Doctoral Foundation of China(Nos.2007BS08013 and BS2012NY011)
文摘When humic acid (HA) and phosphorus (P) fertilizer are simultaneously applied to soil, HA may affect the movement of P. A laboratory incubation experiment was conducted to quantify the effects of a commercial HA product co-applied with monocalcium phosphate (MCP) on the distance of P movement and the concentration of P in various forms at different distances from the P fertilizer application site in a calcareous soil from northern China. Fertilizer MCP (at a rate equivalent to 26.6 kg P ha-1 ) was applied alone or in combination with HA (at 254.8 kg HA ha-1 ) to the surface of soil packed in cylinders (150 mm high and 50 mm internal diameter), and then incubated at 320 g kg-1 moisture content for 7 and 28 d periods. Extraction and analysis of each 2 mm soil layer in columns showed that the addition of HA to MCP increased the distance of P movement and the concentrations of water-extractable P, acid-extractable P and Olsen P in soil. The addition of HA to MCP could enhance P availability by increasing the distance of P movement and the concentration of extractable P in soil surrounding the P fertilizer.