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用于流动反应器中甲烷氧化偶联制碳氢化合物的铂和氧化铜修饰的二氧化钛光催化剂。

Platinum- and CuO -Decorated TiO Photocatalyst for Oxidative Coupling of Methane to C Hydrocarbons in a Flow Reactor.

作者信息

Li Xiyi, Xie Jijia, Rao Heng, Wang Chao, Tang Junwang

机构信息

Solar Energy and Advanced Materials Research Group, Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK.

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, China.

出版信息

Angew Chem Int Ed Engl. 2020 Oct 26;59(44):19702-19707. doi: 10.1002/anie.202007557. Epub 2020 Jul 16.

Abstract

Oxidative coupling of methane (OCM) is considered one of the most promising catalytic technologies to upgrade methane. However, C products (C H /C H ) from conventional methane conversion have not been produced commercially owing to competition from overoxidation and carbon accumulation at high temperatures. Herein, we report the codeposition of Pt nanoparticles and CuO clusters on TiO (PC-50) and use of the resulting photocatalyst for OCM in a flow reactor operated at room temperature under atmospheric pressure for the first time. The optimized Cu Pt /PC-50 sample showed a highest yield of C product of 6.8 μmol h at a space velocity of 2400 h , more than twice the sum of the activity of Pt/PC-50 (1.07 μmol h ) and Cu/PC-50 (1.9 μmol h ), it might also be the highest among photocatalytic methane conversions reported so far under atmospheric pressure. A high C selectivity of 60 % is also comparable to that attainable by conventional high-temperature (>943 K) thermal catalysis. It is proposed that Pt functions as an electron acceptor to facilitate charge separation, while holes could transfer to CuO to avoid deep dehydrogenation and the overoxidation of C products.

摘要

甲烷氧化偶联(OCM)被认为是升级甲烷最具前景的催化技术之一。然而,由于高温下过氧化和积碳的竞争,传统甲烷转化产生的C产物(C₂H₄/C₂H₆)尚未实现商业化生产。在此,我们首次报道了在TiO₂(PC-50)上共沉积Pt纳米颗粒和CuO团簇,并将所得光催化剂用于在室温常压下运行的流动反应器中的OCM。优化后的CuₓPt₁₋ₓ/PC-50样品在空速为2400 h⁻¹时,C产物的最高产率为6.8 μmol h⁻¹,是Pt/PC-50(1.07 μmol h⁻¹)和Cu/PC-50(1.9 μmol h⁻¹)活性总和的两倍多,这也可能是迄今为止报道的常压下光催化甲烷转化中的最高值。60%的高C₂选择性也与传统高温(>943 K)热催化所能达到的选择性相当。有人提出,Pt作为电子受体促进电荷分离,而空穴可以转移到CuO上以避免深度脱氢和C产物的过氧化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dbca/7689917/ed30f2070550/ANIE-59-19702-g001.jpg

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