Electrochemical co-reduction of nitrate(NO_(3)^(-))and carbon dioxide(CO_(2))has been widely regarded as a promising route to produce urea under ambient conditions,however the yield rate of urea has remained limited.H...Electrochemical co-reduction of nitrate(NO_(3)^(-))and carbon dioxide(CO_(2))has been widely regarded as a promising route to produce urea under ambient conditions,however the yield rate of urea has remained limited.Here,we report an atomically ordered intermetallic pallium-zinc(PdZn)electrocatalyst comprising a high density of PdZn pairs for boosting urea electrosynthesis.It is found that Pd and Zn are responsible for the adsorption and activation of NO_(3)^(-)and CO_(2),respectively,and thus the co-adsorption and co-activation NO_(3)^(-)and CO_(2) are achieved in ordered PdZn pairs.More importantly,the ordered and well-defined PdZn pairs provide a dual-site geometric structure conducive to the key C-N coupling with a low kinetical barrier,as demonstrated on both operando measurements and theoretical calculations.Consequently,the PdZn electrocatalyst displays excellent performance for the co-reduction to generate urea with a maximum urea Faradaic efficiency of 62.78%and a urea yield rate of 1274.42μg mg^(-1) h^(-1),and the latter is 1.5-fold larger than disordered pairs in PdZn alloys.This work paves new pathways to boost urea electrosynthesis via constructing ordered dual-metal pairs.展开更多
Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)...Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.展开更多
Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environme...Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environmental problems. With the increasing global demand for environmental protection and sustainable development, it is much necessary to develop novel and clean methods for the synthesis of urea.Electrocatalysis provides an efficient and renewable synthesis route that can directly produce urea at room temperature and atmospheric pressure by the coupling of CO_(2) and nitrogenous molecules. In this review, we summarized the most recent advances in electrochemical synthesis of urea via CAN coupling systematically, focusing on the coupling of CO_(2) and different nitrogen sources. And the associated coupling mechanism, catalysts optimization, and electrolyzer design are well discussed. Moreover, the challenges and future directions for electrocatalytic CAN coupling are prospected. This review will provide timely and valuable guidance for others and attract more interests to promote the development of electrochemical synthesis of urea or other valuable chemicals containing CAN bond.展开更多
At room temperature(25 ℃), urea and ferric chloride hexahydrate(system Ⅰ) or f erric nitrate nonahydrate(system Ⅱ) in a mole ratio of 6∶1 were mixed and ground finely in an agate mortar for 6 hours, a direc t soli...At room temperature(25 ℃), urea and ferric chloride hexahydrate(system Ⅰ) or f erric nitrate nonahydrate(system Ⅱ) in a mole ratio of 6∶1 were mixed and ground finely in an agate mortar for 6 hours, a direc t solid state reaction occurred. IR and elemental analysis confirmed the products obtained are the com- plexes of urea with ir on(Ⅲ).展开更多
基金supported by the National Natural Science Foundation of China(22379100,U21A20312)the Shenzhen Science and Technology Program(Grant No.20231121200418001)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(2022B1515120084)the Key Project of Department of Education of Guangdong Province(2023ZDZX3020)。
文摘Electrochemical co-reduction of nitrate(NO_(3)^(-))and carbon dioxide(CO_(2))has been widely regarded as a promising route to produce urea under ambient conditions,however the yield rate of urea has remained limited.Here,we report an atomically ordered intermetallic pallium-zinc(PdZn)electrocatalyst comprising a high density of PdZn pairs for boosting urea electrosynthesis.It is found that Pd and Zn are responsible for the adsorption and activation of NO_(3)^(-)and CO_(2),respectively,and thus the co-adsorption and co-activation NO_(3)^(-)and CO_(2) are achieved in ordered PdZn pairs.More importantly,the ordered and well-defined PdZn pairs provide a dual-site geometric structure conducive to the key C-N coupling with a low kinetical barrier,as demonstrated on both operando measurements and theoretical calculations.Consequently,the PdZn electrocatalyst displays excellent performance for the co-reduction to generate urea with a maximum urea Faradaic efficiency of 62.78%and a urea yield rate of 1274.42μg mg^(-1) h^(-1),and the latter is 1.5-fold larger than disordered pairs in PdZn alloys.This work paves new pathways to boost urea electrosynthesis via constructing ordered dual-metal pairs.
基金supported by the Research Grants Council(26206115,16304821 and 16309418)the Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(SMSEGL20SC01)+2 种基金the Innovation and Technology Commission(grant no.ITC-CNERC14EG03)of the Hong Kong Special Administrative Regionthe Hong Kong Postdoctoral Fellowship Scheme(HKUST PDFS2021-4S12 and HKUST PDFS2021-6S08)the support from the Shenzhen fundamental research funding(JCYJ20210324115809026,20200925154115001,JCYJ20200109141216566)。
文摘Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.
基金National Natural Science Foundation of China (No. 22202065, 22075092 and U21A20500)。
文摘Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environmental problems. With the increasing global demand for environmental protection and sustainable development, it is much necessary to develop novel and clean methods for the synthesis of urea.Electrocatalysis provides an efficient and renewable synthesis route that can directly produce urea at room temperature and atmospheric pressure by the coupling of CO_(2) and nitrogenous molecules. In this review, we summarized the most recent advances in electrochemical synthesis of urea via CAN coupling systematically, focusing on the coupling of CO_(2) and different nitrogen sources. And the associated coupling mechanism, catalysts optimization, and electrolyzer design are well discussed. Moreover, the challenges and future directions for electrocatalytic CAN coupling are prospected. This review will provide timely and valuable guidance for others and attract more interests to promote the development of electrochemical synthesis of urea or other valuable chemicals containing CAN bond.
文摘At room temperature(25 ℃), urea and ferric chloride hexahydrate(system Ⅰ) or f erric nitrate nonahydrate(system Ⅱ) in a mole ratio of 6∶1 were mixed and ground finely in an agate mortar for 6 hours, a direc t solid state reaction occurred. IR and elemental analysis confirmed the products obtained are the com- plexes of urea with ir on(Ⅲ).
