دورية أكاديمية
N and OH-Immobilized Cu 3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO 2 Electromethanation in Bicontinuous Mesochannels
| العنوان: | N and OH-Immobilized Cu 3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO 2 Electromethanation in Bicontinuous Mesochannels |
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| المؤلفون: | Fuping Pan, Lingzhe Fang, Boyang Li, Xiaoxuan Yang, Thomas O’Carroll, Haoyang Li, Tao Li, Guofeng Wang, Kai-Jie Chen, Gang Wu |
| سنة النشر: | 2024 |
| مصطلحات موضوعية: | Biochemistry, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Information Systems not elsewhere classified, unprecedented faradaic efficiency, range mesochannels offer, hydrogen evolution reaction, extensively used fuel, create favorable microenvironments, level current density, high energy barrier, catalyst design principles, carbon support ’, supported cu catalysts, sites possess moderate, bicontinuous mesochannels cu, active sites embedded, 4 , 3 , steer complex co, favor deep co, co adsorption affinity, engineering pore architectures, 2 , situ constructed n, design carbon, block <, low barrier, atomic level |
| الوصف: | Cu-based catalysts hold promise for electrifying CO 2 to produce methane, an extensively used fuel. However, the activity and selectivity remain insufficient due to the lack of catalyst design principles to steer complex CO 2 reduction pathways. Herein, we develop a concept to design carbon-supported Cu catalysts by regulating Cu active sites’ atomic-scale structures and engineering the carbon support’s mesoscale architecture. This aims to provide a favorable local reaction microenvironment for a selective CO 2 reduction pathway to methane. In situ X-ray absorption and Raman spectroscopy analyses reveal the dynamic reconstruction of nitrogen and hydroxyl-immobilized Cu 3 (N,OH-Cu 3 ) clusters derived from atomically dispersed Cu–N 3 sites under realistic CO 2 reduction conditions. The N,OH-Cu 3 sites possess moderate *CO adsorption affinity and a low barrier for *CO hydrogenation, enabling intrinsically selective CO 2 -to-CH 4 reduction compared to the C–C coupling with a high energy barrier. Importantly, a block copolymer-derived carbon fiber support with interconnected mesopores is constructed. The unique long-range mesochannels offer an H 2 O-deficient microenvironment and prolong the transport path for the CO intermediate, which could suppress the hydrogen evolution reaction and favor deep CO 2 reduction toward methane formation. Thus, the newly developed catalyst consisting of in situ constructed N,OH-Cu 3 active sites embedded into bicontinuous carbon mesochannels achieved an unprecedented Faradaic efficiency of 74.2% for the CO 2 reduction to methane at an industry-level current density of 300 mA cm –2 . This work explores effective concepts for steering desirable reaction pathways in complex interfacial catalytic systems via modulating active site structures at the atomic level and engineering pore architectures of supports on the mesoscale to create favorable microenvironments. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | unknown |
| العلاقة: | https://figshare.com/articles/journal_contribution/N_and_OH-Immobilized_Cu_sub_3_sub_Clusters_In_Situ_Reconstructed_from_Single-Metal_Sites_for_Efficient_CO_sub_2_sub_Electromethanation_in_Bicontinuous_Mesochannels/24939572Test |
| DOI: | 10.1021/jacs.3c10524.s001 |
| الإتاحة: | https://doi.org/10.1021/jacs.3c10524.s001Test https://figshare.com/articles/journal_contribution/N_and_OH-Immobilized_Cu_sub_3_sub_Clusters_In_Situ_Reconstructed_from_Single-Metal_Sites_for_Efficient_CO_sub_2_sub_Electromethanation_in_Bicontinuous_Mesochannels/24939572Test |
| حقوق: | CC BY-NC 4.0 |
| رقم الانضمام: | edsbas.C6A9D466 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/jacs.3c10524.s001 |
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