Electrocatalytic co-reduction of CO_(2)and nitrate offers an attractive and sustainable pathway for urea synthesis,as it enables the simultaneous valorization of nitrogenous waste and CO_(2)into value-added chemicals....Electrocatalytic co-reduction of CO_(2)and nitrate offers an attractive and sustainable pathway for urea synthesis,as it enables the simultaneous valorization of nitrogenous waste and CO_(2)into value-added chemicals.However,achieving ambient and high-performance urea electrosynthesis remains a persistent challenge,as it requires the simultaneous activation of CO_(2)and efficient H_(2)O dissociation to supply active^(*)H for^(*)NO x hydrogenation—ultimately forming key Cand N-containing intermediates necessary for effective C-N coupling.The stringent,sequential nature of the reaction requirements continues to present substantial challenges for the rational design of advanced multifunctional catalysts.Herein,we report a creative two-in-one catalyst,bifunctional Pd-single-atom-modified Cu(Pd_(1)Cu)nanorods,to synergistically promote the adsorption and stepwise activation of dual species,that is,CO_(2)and H_(2)O,thereby effectively steering the reaction pathway toward the highly selective synthesis of urea.By integrating experimental evidence,in situ spectroscopy,and computational analyses,we clearly disclose that the atomically dispersed Pd sites kinetically favor the co-generation of^(*)CO and^(*)NH_(2)(via H_(2)O dissociation-driven proton transfer),thereby forming an optimal intermediate balance that facilitates urea synthesis.More importantly,the rationally designed Pd_(1)Cu leverages dual metal active sites to enhance C-N coupling via combined electronic and geometric effects,substantially lowering the reaction energy barrier and improving selectivity toward urea.展开更多
The reductive cross-coupling between C(aryl)—O and Si—Cl bonds is of much importance as a valuable strategy for the construction of C(aryl)—Si bonds but has remained a great challenge.Herein,we report a reductive c...The reductive cross-coupling between C(aryl)—O and Si—Cl bonds is of much importance as a valuable strategy for the construction of C(aryl)—Si bonds but has remained a great challenge.Herein,we report a reductive cross-coupling of diaryl ethers and chlorosilanes via strong electrophilic C(aryl)—O and Si—Cl bonds cleavage by iron catalysis,which constitutes an efficient protocol for the synthesis of a range of functionalized arylsilanes.The combination of low cost FeCl2 as the precatalyst and iPrMgCl as the reductant shows high activity in the successive cleavage of unactivated C(aryl)—O bonds of diaryl ethers and strong electrophilic Si—Cl bonds of chlorosilanes,allowing their cross-coupling in a reductive fashion.The low-valent iron species generated in situ by reduction of FeCl2 with iPrMgCl was proposed,which prefers to initially cleavage the C(aryl)—O bond of diaryl ethers with the chelation help of an o-amide auxiliary.展开更多
基金the funding support from the National Natural Science Foundation of China(22373080)Fujian Pro-vincial Natural Science Foundation of China(2024J08008)+6 种基金the funding support from the National Natural Science Foundation of China(22402163)Fujian Provincial Science and Technology Program for International Cooperation(2025I0002)Natural Science Foundation of Xiamen,China(3502Z202472001)the funding support from the National Natural Science Foundation of China(22078274)the funding support from the Funda-mental Research Funds for the Central Universities(20720240054)Nan-Qiang Youth Scholar Program of Xiamen UniversityXiaomi Young Talents Program/Xiaomi Foundation。
文摘Electrocatalytic co-reduction of CO_(2)and nitrate offers an attractive and sustainable pathway for urea synthesis,as it enables the simultaneous valorization of nitrogenous waste and CO_(2)into value-added chemicals.However,achieving ambient and high-performance urea electrosynthesis remains a persistent challenge,as it requires the simultaneous activation of CO_(2)and efficient H_(2)O dissociation to supply active^(*)H for^(*)NO x hydrogenation—ultimately forming key Cand N-containing intermediates necessary for effective C-N coupling.The stringent,sequential nature of the reaction requirements continues to present substantial challenges for the rational design of advanced multifunctional catalysts.Herein,we report a creative two-in-one catalyst,bifunctional Pd-single-atom-modified Cu(Pd_(1)Cu)nanorods,to synergistically promote the adsorption and stepwise activation of dual species,that is,CO_(2)and H_(2)O,thereby effectively steering the reaction pathway toward the highly selective synthesis of urea.By integrating experimental evidence,in situ spectroscopy,and computational analyses,we clearly disclose that the atomically dispersed Pd sites kinetically favor the co-generation of^(*)CO and^(*)NH_(2)(via H_(2)O dissociation-driven proton transfer),thereby forming an optimal intermediate balance that facilitates urea synthesis.More importantly,the rationally designed Pd_(1)Cu leverages dual metal active sites to enhance C-N coupling via combined electronic and geometric effects,substantially lowering the reaction energy barrier and improving selectivity toward urea.
基金financial support from the National Natural Science Foundation of China(21901206)Postdoctoral Science Foundation of China(2022M712589)+2 种基金General key R&D Projects in Shaanxi Province(2023-YBGY-321)Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0826)Fundamental Research Funds for the Central Universities and the Haihe Laboratory of Sustainable Chemical Transformation.
文摘The reductive cross-coupling between C(aryl)—O and Si—Cl bonds is of much importance as a valuable strategy for the construction of C(aryl)—Si bonds but has remained a great challenge.Herein,we report a reductive cross-coupling of diaryl ethers and chlorosilanes via strong electrophilic C(aryl)—O and Si—Cl bonds cleavage by iron catalysis,which constitutes an efficient protocol for the synthesis of a range of functionalized arylsilanes.The combination of low cost FeCl2 as the precatalyst and iPrMgCl as the reductant shows high activity in the successive cleavage of unactivated C(aryl)—O bonds of diaryl ethers and strong electrophilic Si—Cl bonds of chlorosilanes,allowing their cross-coupling in a reductive fashion.The low-valent iron species generated in situ by reduction of FeCl2 with iPrMgCl was proposed,which prefers to initially cleavage the C(aryl)—O bond of diaryl ethers with the chelation help of an o-amide auxiliary.
