دورية أكاديمية
Electrocatalytic Urea Synthesis via N 2 Dimerization and Universal Descriptor
| العنوان: | Electrocatalytic Urea Synthesis via N 2 Dimerization and Universal Descriptor |
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| المؤلفون: | Junxian Liu, Xingshuai Lv, Yandong Ma, Sean C. Smith, YuanTong Gu, Liangzhi Kou |
| سنة النشر: | 2023 |
| مصطلحات موضوعية: | Biophysics, Biochemistry, Cell Biology, Molecular Biology, Physiology, Developmental Biology, Chemical Sciences not elsewhere classified, Information Systems not elsewhere classified, universal guiding principle, harsh industrial processes, despite considerable efforts, competing side reactions, urea electrochemical synthesis, specific urea precursor, highly active catalysts, 4 , 3 , 2 , electrocatalytic urea formation, two n atoms, urea formation, urea catalysts, substrate atoms, metal atoms, − 0, φ ), work advances, sustainable alternative, simple descriptor, quantitatively describe |
| الوصف: | Electrocatalytic urea synthesis through N 2 + CO 2 coreduction and C–N coupling is a promising and sustainable alternative to harsh industrial processes. Despite considerable efforts, limited progress has been made due to the challenges of breaking inert NN bonds for C–N coupling, competing side reactions, and the absence of theoretical principles guiding catalyst design. In this study, we propose a mechanism for highly electrocatalytic urea synthesis using two adsorbed N 2 molecules and CO as nitrogen and carbon sources, respectively. This mechanism circumvents the challenging step of NN bond breaking and selective CO 2 to CO reduction, as the free CO molecule inserts into dimerized *N 2 and binds concurrently with two N atoms, forming a specific urea precursor *NNCONN* with both thermodynamic and kinetic feasibility. Through the proposed mechanism, Ti 2 @C 4 N 3 and V 2 @C 4 N 3 are identified as highly active catalysts for electrocatalytic urea formation, exhibiting low onset potentials of −0.741 and −0.738 V, respectively. Importantly, taking transition metal atoms anchored on porous graphite-like carbonitride (TM 2 @C 4 N 3 ) as prototypes, we introduce a simple descriptor, namely, effective d electron number (Φ), to quantitatively describe the structure–activity relationships for urea formation. This descriptor incorporates inherent atomic properties of the catalyst, such as the number of d electrons, the electronegativity of the metal atoms, and the generalized electronegativity of the substrate atoms, making it potentially applicable to other urea catalysts. Our work advances the comprehension of mechanisms and provides a universal guiding principle for catalyst design in urea electrochemical synthesis. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | unknown |
| العلاقة: | https://figshare.com/articles/journal_contribution/Electrocatalytic_Urea_Synthesis_via_N_sub_2_sub_Dimerization_and_Universal_Descriptor/24807306Test |
| DOI: | 10.1021/acsnano.3c10451.s001 |
| الإتاحة: | https://doi.org/10.1021/acsnano.3c10451.s001Test https://figshare.com/articles/journal_contribution/Electrocatalytic_Urea_Synthesis_via_N_sub_2_sub_Dimerization_and_Universal_Descriptor/24807306Test |
| حقوق: | CC BY-NC 4.0 |
| رقم الانضمام: | edsbas.E62B244C |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acsnano.3c10451.s001 |
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