Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,t...Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.展开更多
Calcium looping realizes CO_(2)capture via the cyclic calcination/carbonation of CaO.The combustion of fuel supplies energy for the calciner.It is unavoidable that some unburned char in the calciner flows into the car...Calcium looping realizes CO_(2)capture via the cyclic calcination/carbonation of CaO.The combustion of fuel supplies energy for the calciner.It is unavoidable that some unburned char in the calciner flows into the carbonator,generating CO due to the hypoxic atmosphere in the carbonator.CO can reduce NO in the flue gases from coal-fired power plants.In this work,NO removal performance of CO in the carbonation stage of calcium looping for CO_(2)capture was investigated in a bubbling fluidized bed reactor.The effects of carbonation temperature,CO concentration,CO_(2)capture,type of CaO,number of CO_(2)capture cycles and presence of char on NO removal by CO in carbonation stage of calcium looping were discussed.CaO possesses an efficient catalytic effect on NO removal by CO.High temperature and high CO concentration lead to high NO removal efficiency of CO in the presence of CaO.Taking account of better NO removal and CO_(2)capture,the optimal carbonation temperature is 650℃.The carbonation of CaO reduces the catalytic activity of CaO for NO removal by CO due to the formation of CaCO_(3).Besides,the catalytic performance of CaO on NO removal by CO gradually decreases with the number of CO_(2)capture cycles.This is because the sintering of CaO leads to the fusion of CaO grains and blockage of pores in CaO,hindering the diffusion of NO and CO.The high CaO content and porous structure of calcium-based sorbents are beneficial for NO removal by CO.The presence of char promotes NO removal by CO in the carbonator.CO_(2)/NO removal efficiencies can reach above 90%.The efficient simultaneous NO and CO_(2)removal by CO and CaO in the carbonation step of the calcium looping seems promising.展开更多
The increase of atmospheric carbon dioxide（CO_2） concentration adversely affect several quality traits of rice grains, but the biochemical mechanism remains unclear. The objectives of this study were to determine ho...The increase of atmospheric carbon dioxide（CO_2） concentration adversely affect several quality traits of rice grains, but the biochemical mechanism remains unclear. The objectives of this study were to determine how changes in the source-sink relationship affected rice quality. Source-sink manipulation was achieved by free-air CO_2 enrichment from tillering to maturity and partial removal of spikelet at anthesis using a japonica rice cultivar Wuyunjing 23. Enrichment with CO_2 decreased the head rice percentage and protein concentration of milled rice, but increased the grain chalkiness. In contrast, spikelet removal resulted in a dramatic increase in the head rice percentage and protein concentration, and much less grain chalkiness. Neither CO_2 enrichment nor spikelet removal affected the starch content, but the distribution of starch granule size showed distinct treatment effects. O n average, spikelet removal decreased the percentage of starch granules of diameter 〉10 and 5–10 μm by 23.6 and 5.6%, respectively, and increased those with a diameter of 2–5 and 〈2 μm by 4.6 and 3.3%, respectively. In contrast, CO_2 elevation showed an opposite response： increasing the proportion of large starch granules（〉5 μm） and decreasing that of 〈5 μm. The starch pasting properties were affected by spikelet removal much more than by CO_2 elevation. These results indicated that the protein concentration and starch granule size played a role in chalkiness formation under these experimental conditions.展开更多
基金the financial support of the Training Program of the Major Research Plan of the National Natural Science Foundation of China(92061124)the National Natural Science Foundation of China(21975292,21978331,22068008,and 52101186)+3 种基金the Guangdong Basic and Applied Basic Research Foundation(2021A1515010167 and 2022A1515011196)the Guangzhou Key R&D Program/Plan Unveiled Flagship Project(20220602JBGS02)the Guangzhou Basic and Applied Basic Research Project(202201011449)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202220 and FC202216)。
文摘Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.
基金Financial supports from the National Natural Science Foundation of China(51876105)the Joint Foundation of National Natural Science Foundation of China and Shanxi Province for coal-based low carbon(U1510130)+2 种基金Shandong Provincial Natural Science Foundation(ZR2020ME188)the Fundamental Research Funds of Shandong University(2018JC039)the program for Outstanding PhD candidate of Shandong University。
文摘Calcium looping realizes CO_(2)capture via the cyclic calcination/carbonation of CaO.The combustion of fuel supplies energy for the calciner.It is unavoidable that some unburned char in the calciner flows into the carbonator,generating CO due to the hypoxic atmosphere in the carbonator.CO can reduce NO in the flue gases from coal-fired power plants.In this work,NO removal performance of CO in the carbonation stage of calcium looping for CO_(2)capture was investigated in a bubbling fluidized bed reactor.The effects of carbonation temperature,CO concentration,CO_(2)capture,type of CaO,number of CO_(2)capture cycles and presence of char on NO removal by CO in carbonation stage of calcium looping were discussed.CaO possesses an efficient catalytic effect on NO removal by CO.High temperature and high CO concentration lead to high NO removal efficiency of CO in the presence of CaO.Taking account of better NO removal and CO_(2)capture,the optimal carbonation temperature is 650℃.The carbonation of CaO reduces the catalytic activity of CaO for NO removal by CO due to the formation of CaCO_(3).Besides,the catalytic performance of CaO on NO removal by CO gradually decreases with the number of CO_(2)capture cycles.This is because the sintering of CaO leads to the fusion of CaO grains and blockage of pores in CaO,hindering the diffusion of NO and CO.The high CaO content and porous structure of calcium-based sorbents are beneficial for NO removal by CO.The presence of char promotes NO removal by CO in the carbonator.CO_(2)/NO removal efficiencies can reach above 90%.The efficient simultaneous NO and CO_(2)removal by CO and CaO in the carbonation step of the calcium looping seems promising.
基金funded jointly by the National Natural Science Foundation of China(31171460,31371563,31571597,31471437,31261140364)the Major Fundamental Research Program of Natural Science Foundation of Jiangsu Higher Education Institutions,China(11KJA210003)+2 种基金the Jiangsu Planned Projects for Postdoctoral Research Funds,China(1501077C)the China Postdoctoral Science Foundation(2015M581870)the Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘The increase of atmospheric carbon dioxide（CO_2） concentration adversely affect several quality traits of rice grains, but the biochemical mechanism remains unclear. The objectives of this study were to determine how changes in the source-sink relationship affected rice quality. Source-sink manipulation was achieved by free-air CO_2 enrichment from tillering to maturity and partial removal of spikelet at anthesis using a japonica rice cultivar Wuyunjing 23. Enrichment with CO_2 decreased the head rice percentage and protein concentration of milled rice, but increased the grain chalkiness. In contrast, spikelet removal resulted in a dramatic increase in the head rice percentage and protein concentration, and much less grain chalkiness. Neither CO_2 enrichment nor spikelet removal affected the starch content, but the distribution of starch granule size showed distinct treatment effects. O n average, spikelet removal decreased the percentage of starch granules of diameter 〉10 and 5–10 μm by 23.6 and 5.6%, respectively, and increased those with a diameter of 2–5 and 〈2 μm by 4.6 and 3.3%, respectively. In contrast, CO_2 elevation showed an opposite response： increasing the proportion of large starch granules（〉5 μm） and decreasing that of 〈5 μm. The starch pasting properties were affected by spikelet removal much more than by CO_2 elevation. These results indicated that the protein concentration and starch granule size played a role in chalkiness formation under these experimental conditions.
