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共酞菁/氮化硼 Z 型光催化剂中掺杂剂和缺陷的协同作用促进光催化 CO 还原反应。

Synergistic Functionality of Dopants and Defects in Co-Phthalocyanine/B-CN Z-Scheme Photocatalysts for Promoting Photocatalytic CO Reduction Reactions.

机构信息

School of Physics and Electronics, Central South University, Changsha, 410083, P. R. China.

Key Laboratory of Functional Inorganic Material Chemistry, The Ministry of Education of the Peoples Republic of China, Heilongjiang University, Harbin, 150080, P. R. China.

出版信息

Small. 2023 Jun;19(25):e2208179. doi: 10.1002/smll.202208179. Epub 2023 Mar 19.

DOI:10.1002/smll.202208179
PMID:36935369
Abstract

The realization of solar-light-driven CO  reduction reactions (CO RR) is essential for the commercial development of renewable energy modules and the reduction of global CO emissions. Combining experimental measurements and theoretical calculations, to introduce boron dopants and nitrogen defects in graphitic carbon nitride (g-C N ), sodium borohydride is simply calcined with the mixture of g-C N (CN), followed by the introduction of ultrathin Co phthalocyanine through phosphate groups. By strengthening H-bonding interactions, the resultant CoPc/P-BNDCN nanocomposite showed excellent photocatalytic CO reduction activity, releasing 197.76 and 130.32 µmol h  g CO and CH , respectively, and conveying an unprecedented 10-26-time improvement under visible-light irradiation. The substantial tuning is performed towards the conduction and valance band locations by B-dopants and N-defects to modulate the band structure for significantly accelerated CO RR. Through the use of ultrathin metal phthalocyanine assemblies that have a lot of single-atom sites, this work demonstrates a sustainable approach for achieving effective photocatalytic CO activation. More importantly, the excellent photoactivity is attributed to the fast charge separation via Z-scheme transfer mechanism formed by the universally facile strategy of dimension-matched ultrathin (≈4 nm) metal phthalocyanine-assisted nanocomposites.

摘要

实现太阳能驱动的二氧化碳还原反应(CO RR)对于可再生能源模块的商业开发和全球 CO 排放的减少至关重要。本研究通过实验测量和理论计算相结合,在石墨相氮化碳(g-C 3 N 4 )中引入硼掺杂和氮缺陷,将 g-C 3 N 4 (CN)与硼氢化钠简单煅烧,然后通过磷酸盐基团引入超薄的钴酞菁。通过加强氢键相互作用,所得的 CoPc/P-BNDCN 纳米复合材料表现出优异的光催化 CO 还原活性,分别释放出 197.76 和 130.32 µmol h 1 g CO 和 CH 4 ,在可见光照射下,其活性提高了前所未有的 10-26 倍。B 掺杂和 N 缺陷对导带和价带位置进行了大量的调谐,从而调节了能带结构,显著加速了 CO RR。通过使用具有大量单原子位点的超薄金属酞菁组装体,本工作展示了一种实现有效光催化 CO 活化的可持续方法。更重要的是,优异的光活性归因于通过普遍易于实现的尺寸匹配的超薄(≈4nm)金属酞菁辅助纳米复合材料形成的 Z 型转移机制实现的快速电荷分离。

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