Ningning Xu , Chenyu Li , Xinyan Lin , Xiaotong Lin , Xiaoyang Zhao , Junmin Nan , Xin Xiao
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引用次数: 0
摘要
事实证明,在光催化剂中引入氧空位(OVs)是促进二氧化碳还原的成功策略。然而,挑战在于如何获得长期稳定、高度分散且浓度可调的氧空位。在此,我们通过原位掺杂阴离子的方法,为模型半导体 Bi2O2CO3 开发了一种创新的构型,即 N-Bi(3+x)+--OV。这种结构使合成光催化剂表现出卓越的二氧化碳光还原性能,具有约 100% 的二氧化碳选择性和显著的长期稳定性。实验研究和密度泛函理论(DFT)计算表明,在[Bi2O2]2+ 结构单元中均匀地用 N3- 取代 O2-,可提高 Bi 的化合价,拉长附近的 Bi─O 键,释放晶格 O,改善 CO2 吸收,并降低形成临界中间体 *COOH 的能垒。这项研究为开发可靠的缺陷型半导体及其催化应用提供了新的见解和潜在机会。
Design of atomically dispersed N-Bi(3+x)+--OV sites in ultrathin Bi2O2CO3 nanosheets for efficient and durable visible-light-driven CO2 reduction
The introduction of oxygen vacancies (OVs) into photocatalysts has proven to be a successful tactic to boost CO2 reduction. However, the challenge lies in acquiring OV sites that are stable in the long term, highly dispersed, and tunable in concentration. Herein, an innovative configuration, referred to as N-Bi(3+x)+--OV, was developed for the model semiconductor Bi2O2CO3 via an in situ anion doping approach. The structure enables the synthetic photocatalyst to exhibit superb CO2 photoreduction performance, with approximately 100% CO selectivity and remarkable long-term stability. Experimental studies and density functional theory (DFT) calculations show that replacing O2- with N3- uniformly in the [Bi2O2]2+ structural unit increases the chemical valence of Bi, elongates nearby Bi─O bonds, releases lattice O, improves CO2 absorption, and decreases the energy barrier for the formation of the critical intermediate *COOH. This study offers new insights and potential opportunities for the development of reliable defect-type semiconductors and their catalytic applications.
期刊介绍:
Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications.
Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.