RESUMO
Photocatalysis has the advantages of practical, sustainable and environmental protection, so it plays a significant role in energy transformation and environmental utilization. CeO2 has attracted widespread attention for its unique 4 f electrons, rich defect structures, high oxygen storage capacity and great chemical stability. In this paper, we review the structure of CeO2 and the common methods for the preparation of CeO2-based composites in the first part. In particular, we highlight the co-precipitation method, template method, and sol-gel method methods. Then, in the second part, we introduce the application of CeO2-based composites in photocatalysis, including photocatalytic CO2 reduction, hydrogen production, degradation, selective organic reaction, and photocatalytic nitrogen fixation. In addition, we discuss several modification techniques to improve the photocatalytic performance of CeO2-based composites, such as elemental doping, defect engineering, constructing heterojunction and morphology regulation. Finally, the challenges faced by CeO2-based composites are analyzed and their development prospects are prospected. This review provides a systematic summary of the recent advance of CeO2-based composites in the field of photocatalysis, which can provide useful references for the rational design of efficient CeO2-based composite photocatalysts for sustainable development.
RESUMO
Singlet oxygen (1 O2 ) is an excellent reactive oxygen species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to the huge dilemma in synthesizing single-site type catalysts, the control and regulation of 1 O2 generation in AOPs is still challenging and the underlying mechanism remains largely obscure. Here, taking advantage of the well-defined and flexibly tunable sites of covalent organic frameworks (COFs), we report the first achievement in precisely regulating ROSs generation in peroxymonosulfate (PMS)-based AOPs by site engineering of COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway with 100 % 1 O2 , whereas biphenyl-based COFs (BPD-COFs) with almost identical structures activate PMS to produce radicals (â OH and SO4 .- ). The BPY-COFs/PMS system delivers boosted performance for selective degradation of target pollutants from water, which is ca. 9.4 times that of its BPD-COFs counterpart, surpassing most reported PMS-based AOPs systems. Mechanism analysis indicated that highly electronegative pyridine-N atoms on BPY-COFs provide extra sites to adsorb the terminal H atoms of PMS, resulting in simultaneous adsorption of O and H atoms of PMS on one pyridine ring, which facilitates the cleavage of its S-O bond to generate 1 O2 .
RESUMO
Singlet oxygen (1O2) is a thrilling active species for selectively oxidating organic substances. However, the efficient and selective generation of 1O2 maintains a great challenge. Here, we develop a donor-acceptor structured g-C3N4 by covalently engineering benzenetricarboxaldehyde (BTA) onto the fringe of g-C3N4. The g-C3N4-BTA exerts high-efficiency 1O2 generation with nearly 100% selectivity via peroxymonosulfate (PMS) photocatalytic activation upon visible light illumination, exhibiting obviously boosted efficiency for selective elimination of atrazine (ATZ). The consequences of experiments and theoretical calculations demonstrate that BTA units serve as electron-withdrawing sites to trap photogenerated electrons and facilitate the adsorption of PMS on the electron-deficient heptazine rings of g-C3N4. As such, PMS can be in-situ oxidated by the photogenerated holes to selectively produce 1O2. Besides, the g-C3N4-BTA/PMS system delivers high stability and strong resistance to the coexisting organic ions and natural organic matter, demonstrating great potential for selectively removing targeted organic contaminants with high efficiency.