Hydroxylamine(NH_(2)OH),a vital but unstable industrial feedstock,is presently prepared under harsh conditions that cause environmental and energy concerns.Here,we report an electrochemical method to prepare oximes,wh...Hydroxylamine(NH_(2)OH),a vital but unstable industrial feedstock,is presently prepared under harsh conditions that cause environmental and energy concerns.Here,we report an electrochemical method to prepare oximes,which serve as precursors for NH_(2)OH after facile hydrolysis.The carbon-supported amorphous Mn electrocatalyst delivers a current density of~100 mA cm^(-2) with a Faradaic efficiency of 40.92%and a yield rate of 0.251 mmol cm^(-2)h^(-1) for formaldoxime(CH_(2)NOH)generation by using nitrate and formaldehyde as reactants.Formaldoxime can be easily released to produce NH_(2)OH via hydrolysis.Impressively,this method exhibits an economic advantage over conventional manufacturing based on techno-economic analysis.A series of control experiments,in situ characterizations,and theoretical simulations unveil the reaction mechanism via the spontaneous reaction between an aldehyde and*NH_(2)OH intermediate derived from nitrate electroreduction.The high activity of Mn originates from its inhibitory effects on the further reduction of key*NH_(2)OH intermediate.This strategy opens a sustainable and green way for NH_(2)OH synthesis under mild conditions using renewable energy.展开更多
Decomposition of hydroxylammonium nitrate (HAN) solution with electrolytic decomposition method has attracted much attention in recent years due to its efficiencies and practicability.However,the phenomenon has not be...Decomposition of hydroxylammonium nitrate (HAN) solution with electrolytic decomposition method has attracted much attention in recent years due to its efficiencies and practicability.However,the phenomenon has not been well-studied till now. By utilizing mathematical model currently available,the effect of water content and power used for decomposition was studied. Experiment data shows that sacrificial material such as copper or aluminum outperforms inert electrodes in the decomposition of HAN solution. In the case of using copper wire to electrolyse HAN solutions, approximately 10 seconds is required to reach 100℃ regardless of concentration of HAN. In tem of power consumption,100W-300W was found to be the range in which decomposition could be triggered effectively using copper wire as electrodes.展开更多
基金supported by the National Natural Science Foundation of China(22271213(B.Z.)and 22071173(Y.Y.))the Haihe Laboratory of Sustainable Chemical Transformationsthe National Postdoctoral Science Foundation of China(2022M722357(Y.W.))。
文摘Hydroxylamine(NH_(2)OH),a vital but unstable industrial feedstock,is presently prepared under harsh conditions that cause environmental and energy concerns.Here,we report an electrochemical method to prepare oximes,which serve as precursors for NH_(2)OH after facile hydrolysis.The carbon-supported amorphous Mn electrocatalyst delivers a current density of~100 mA cm^(-2) with a Faradaic efficiency of 40.92%and a yield rate of 0.251 mmol cm^(-2)h^(-1) for formaldoxime(CH_(2)NOH)generation by using nitrate and formaldehyde as reactants.Formaldoxime can be easily released to produce NH_(2)OH via hydrolysis.Impressively,this method exhibits an economic advantage over conventional manufacturing based on techno-economic analysis.A series of control experiments,in situ characterizations,and theoretical simulations unveil the reaction mechanism via the spontaneous reaction between an aldehyde and*NH_(2)OH intermediate derived from nitrate electroreduction.The high activity of Mn originates from its inhibitory effects on the further reduction of key*NH_(2)OH intermediate.This strategy opens a sustainable and green way for NH_(2)OH synthesis under mild conditions using renewable energy.
基金The authors would like to acknowledge Ministry ofScience,Technology and Innovation Malaysia(MOSTI)eScience Fund for funding the research project(04-05-05-SF0008).
文摘Decomposition of hydroxylammonium nitrate (HAN) solution with electrolytic decomposition method has attracted much attention in recent years due to its efficiencies and practicability.However,the phenomenon has not been well-studied till now. By utilizing mathematical model currently available,the effect of water content and power used for decomposition was studied. Experiment data shows that sacrificial material such as copper or aluminum outperforms inert electrodes in the decomposition of HAN solution. In the case of using copper wire to electrolyse HAN solutions, approximately 10 seconds is required to reach 100℃ regardless of concentration of HAN. In tem of power consumption,100W-300W was found to be the range in which decomposition could be triggered effectively using copper wire as electrodes.
