Development of a Quinolinium/Cobaloxime Dual Photocatalytic System for Oxidative C–C Cross-Couplings via H2 Release

ACS Catalysis ◽  
2021 ◽  
pp. 14148-14158
Author(s):  
Jianbin Li ◽  
Chia-Yu Huang ◽  
Jing-Tan Han ◽  
Chao-Jun Li

Author(s):  
Autumn Flynn ◽  
Kelly McDaniel ◽  
Meredith Hughes ◽  
David Vogt ◽  
Nathan Jui

A photocatalytic system for the dearomative hydroarylation of benzene derivatives has been developed. Using a combination of an organic photoredox catalyst and an amine reductant, this process operates through a reductive radical-polar crossover mechanism where aryl halide reduction triggers a regioselective cyclization event, giving rise to a range of complex spirocyclic cyclohexadienes. This light-driven protocol functions at room temperature in a green solvent system (aq. MeCN), without the need for precious metal-based catalysts or reagents, or the generation of stoichiometric metal byproducts.



1999 ◽  
Vol 40 (4-5) ◽  
pp. 123-130 ◽  
Author(s):  
S. Malato ◽  
J. Blanco ◽  
C. Richter ◽  
B. Milow ◽  
M. I. Maldonado

Particulate suspensions of TiO2 irradiated with natural solar tight in a large experimental plant catalyse the oxidation of organic contaminants. The problem in using TiO2 as a photocatalyst is electron/hole recombination. One strategy for inhibiting e−/h+ recombination is to add other (irreversible) electron acceptors to the reaction. In many highly toxic waste waters where degradation of organic pollutants is the major concern, the addition of an inorganic anion to enhance the organic degradation rate may be justified. For better results, these additives should fulfil the following criteria: dissociate into harmless by-products and lead to the formation of ·OH or other oxidising agents. In this paper, we attempt to demonstrate the optimum conditions for the treatment of commercial pesticide rinsates found in the wastewater produced by a pesticide container recycling plant. The experiments were performed in one of the pilot plants of the largest solar photocatalytic system in Europe, the Detoxification Plants of the Plataforma Solar de Almería (PSA), in Spain. After testing ten different commercial pesticides, results show that peroxydisulphate enhances the photocatalytic miniralization of all of them. This study is part of an extensive project focused on the design of a solar photocatalytic plant for decontamination of agricultural rinsates in Almería (Spain).



2020 ◽  
Vol 01 ◽  
Author(s):  
Diana Sannino ◽  
Vincenzo Vaiano ◽  
Olga Sacco ◽  
Nicola Morante ◽  
Luca De Guglielmo ◽  
...  

Aims: The aim of this work was to investigate the impact of light modulation parameters on the degradation of terephtalic acid, an organic model pollutant, within a heterogeneous photocatalytic system under visible light. For this purpose, a fixed bed photocatalytic reactor, irradiated by white-light LEDs matrix controlled by a system for light dimming, was used. The bed consisted of a nitrogen-doped titania photocatalyst deposited on polystyrene pellets. Background: Wastewater containing TPA can be treated into conventional aerobic biological units. However, the mineralization of TPA is slow and inefficient and its presence influences negatively the biodegradation efficiency because this pollutant inhibits microbial growth. Nowadays innovative technologies named advanced oxidation processes (AOPs), such as heterogeneous photocatalysis with UV and visible light, ozonation, Fenton oxidation have gained popularity for effective organic destruction of TPA from wastewater. The heterogeneous photocatalytic oxidation process of the TPA under visible light is the most advantageous process in terms of both fixed and operating costs. Objective: In this work the successful application of light modulation techniques to degradation of TPA using a photocatalytic system with supported visible active photocatalysts (N-doped TiO2) immobilized on polystyrene pellets was reported. In particular, sinusoidal lighting has been used analyzing the influence of the period of oscillation and the amplitude of the light modulation on the reaction kinetics, in such a way as to minimize the times and energy costs for the process. Methods: To evaluate the influence of light modulation on the efficiency of the TPA removal, a discontinuous system composed by a Recirculating Photocatalytic Fixed Bed Reactor (RPFBR) irradiated by a matrix of white light LEDs was used. The flat geometry of photoreactor guarantees the efficient excitation of photocatalyst. An amount of 250 mL of aqueous solution with initial TPA concentration of 12.5 ppm was applied in the photocatalytic tests lasting 180 min of irradiation fixed or sinusoidal modulated. Results: The results show that the variation of the oscillation period of the sinusoidal modulation has a relevant influence on the photodegradation of TPA and a maximum value of the apparent kinetic constant, 0.0045 min-1 is found when the period of oscillation is 0.24 s. The sinusoidal modulation with optimal amplitude is that with current between 50-200 mA, that shows the highest value of the apparent kinetic constant, equal to 0.0046 min-1. The optimal sinusoidal modulation, as a consequence is with current between 50-200 mA and period of 0.24 s. From the data collected from the tests, it is possible to evaluate the energy cost necessary to obtain the reduction of 90% of the terephthalic acid in 1 m3 of polluted water for each modulation (E E/O ), and compare these values with other tests for TPA degradation reported in the literature. The internal comparison and with the three systems of literature showed the optima sinusoidal modulation of LEDs matrix permits a strong reduction the electrical energy consumption. Conclusion: Photocatalytic tests have demonstrated the improvement of the process energy efficiency using the light modulation technique . A further confirmation of the advantage of light modulation was obtained by comparing the energy costs required for the abatement of 90% of the terephthalic acid in 1m 3 of the photocatalytic system. Finally, a mathematical model for photocatalytic degradation of terephthalic acid within the recirculating fixed bed photocatalytic reactor, irradiated by white-light LEDs was developed.



Author(s):  
Saikumar Manchala ◽  
Ambedkar Gandamalla ◽  
Vempuluru Navakoteswara Rao ◽  
Shankar Muthukonda Venkatakrishnan ◽  
Vishnu Shanker


Author(s):  
Shuangjun Li ◽  
Linglong Chen ◽  
Zhong Ma ◽  
Guisheng Li ◽  
Dieqing Zhang

AbstractThe emission of nitrogen oxides (NOx) increases year by year, causing serious problems to our livelihoods. The photocatalytic oxidation of NOx has attracted more attention recently because of its efficient removal of NOx, especially for low concentrations of NOx. In this review, the mechanism of the photocatalytic oxidation of NOx is described. Then, the recent progress on the development of photocatalysts is reviewed according to the categories of inorganic semiconductors, bismuth-based compounds, nitrogen carbide polymer, and metal organic frameworks (MOFs). In addition, the photoelectrocatalytic oxidation of NOx, a method involving the application of an external voltage on the photocatalytic system to further increase the removal efficiency of NOx, and its progress are summarized. Finally, we outline the remaining challenges and provide our perspectives on the future directions for the photocatalytic oxidation of NOx.



2021 ◽  
Author(s):  
Xiaoluo Bao ◽  
Xiaokun Wang ◽  
Xiangqing Li ◽  
Lixia Qin ◽  
Taiyang Zhang ◽  
...  

It is necessary for the commercialization of sunlight-driven H2 evolution to develop an efficient photocatalytic system whose energy utilization is independent on incident light intensity. Unfortunately, limited attention has been...



2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yanjun Li ◽  
Ziqi Ye ◽  
Yu-Mei Lin ◽  
Yan Liu ◽  
Yumeng Zhang ◽  
...  

AbstractDevelopment of practical deuteration reactions is highly valuable for organic synthesis, analytic chemistry and pharmaceutic chemistry. Deuterodehalogenation of organic chlorides tends to be an attractive strategy but remains a challenging task. We here develop a photocatalytic system consisting of an aryl-amine photocatalyst and a disulfide co-catalyst in the presence of sodium formate as an electron and hydrogen donor. Accordingly, many aryl chlorides, alkyl chlorides, and other halides are converted to deuterated products at room temperature in air (>90 examples, up to 99% D-incorporation). The mechanistic studies reveal that the aryl amine serves as reducing photoredox catalyst to initiate cleavage of the C-Cl bond, at the same time as energy transfer catalyst to induce homolysis of the disulfide for consequent deuterium transfer process. This economic and environmentally-friendly method can be used for site-selective D-labeling of a number of bioactive molecules and direct H/D exchange of some drug molecules.



2021 ◽  
Vol 549 ◽  
pp. 149176
Author(s):  
Chingis Daulbayev ◽  
Fail Sultanov ◽  
Alina V. Korobeinyk ◽  
Mukhtar Yeleuov ◽  
Seitkhan Azat ◽  
...  


2019 ◽  
Vol 385 ◽  
pp. 44-80 ◽  
Author(s):  
Danlian Huang ◽  
Sha Chen ◽  
Guangming Zeng ◽  
Xiaomin Gong ◽  
Chengyun Zhou ◽  
...  


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