Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased ca...Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.展开更多
在水/有机两相中将羰基还原酶SyS1、葡萄糖1-脱氢酶SyGDH和卤代醇脱卤酶CSyHheC偶联催化α-溴代苯乙酮以高效制备(S)-环氧苯乙烷(SO)。第1步反应催化α-溴代苯乙酮不对称还原为(S)-2-溴-1-苯基乙醇((S)-BPE)及NADPH的原位再生,其优化的...在水/有机两相中将羰基还原酶SyS1、葡萄糖1-脱氢酶SyGDH和卤代醇脱卤酶CSyHheC偶联催化α-溴代苯乙酮以高效制备(S)-环氧苯乙烷(SO)。第1步反应催化α-溴代苯乙酮不对称还原为(S)-2-溴-1-苯基乙醇((S)-BPE)及NADPH的原位再生,其优化的反应条件:100 mmol/L磷酸钾缓冲液(p H 8.0)/正己烷(V∶V=4∶6)、40 mmol/Lα-溴代苯乙酮、80 mmol/LD-葡萄糖、0.2 mmol/L NADP+和70 mg/m L E.coli/Sygdh-Sys1湿菌体(共表达SyGDH和SyS1),终体积1.0 m L,35℃反应8 h。第2步反应催化(S)-BPE脱卤闭环为(S)-SO,其反应条件:在上述反应体系中加入磷酸钾缓冲液(p H 8.0)和0.3 U SyHheC,终体积2.0 m L,35℃反应30 min。通过连续2步酶催化反应,终产物(S)-SO的摩尔产率为99%、对映体过量值>99%。展开更多
基金supported by National Natural Science Foundation of China (Nos.52131003 and 42007180)Special Research Assistant Program of Chinese Academy of Science, Natural Science Foundation of Chongqing (No.cstc2020jcyj-msxm X0775)+1 种基金Scientific Research Instrument Development Project of Chinese Academy of Sciences (No.YJKYYQ20200044)Outstanding Scientist of Chongqing Talent Program (No.CQYC20210101288)。
文摘Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.
文摘在水/有机两相中将羰基还原酶SyS1、葡萄糖1-脱氢酶SyGDH和卤代醇脱卤酶CSyHheC偶联催化α-溴代苯乙酮以高效制备(S)-环氧苯乙烷(SO)。第1步反应催化α-溴代苯乙酮不对称还原为(S)-2-溴-1-苯基乙醇((S)-BPE)及NADPH的原位再生,其优化的反应条件:100 mmol/L磷酸钾缓冲液(p H 8.0)/正己烷(V∶V=4∶6)、40 mmol/Lα-溴代苯乙酮、80 mmol/LD-葡萄糖、0.2 mmol/L NADP+和70 mg/m L E.coli/Sygdh-Sys1湿菌体(共表达SyGDH和SyS1),终体积1.0 m L,35℃反应8 h。第2步反应催化(S)-BPE脱卤闭环为(S)-SO,其反应条件:在上述反应体系中加入磷酸钾缓冲液(p H 8.0)和0.3 U SyHheC,终体积2.0 m L,35℃反应30 min。通过连续2步酶催化反应,终产物(S)-SO的摩尔产率为99%、对映体过量值>99%。
