Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
Faculty of Physics, Northeast Normal University, Changchun 130024, China
Instrumental Analysis Center, Yancheng Teachers University, Yancheng 224007, China
Center of excellence for environmental safety and biological effects, Beijing Key Lab for Green Catalysis and Separation, Faculty of Environment and life, Beijing University of Technology, Beijing 100124, China
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Photocatalytic nitrogen fixation reactions usually occur at the solid–liquid–gas three-phase interface, which inevitably makes the hydrogen production reaction compete with the nitrogen fixation reaction, and it is a key scientific issue to make the nitrogen fixation reaction dominant in the competing reaction. In this contribution, the structure–effect relationship between surface hydrophobicity and the performance of ammonia synthesis was systematically investigated by using alkyl acids with different carbon chain lengths to modify the surface of defective TiO2. The experimental results show that the hydrogen evolution reaction is significantly suppressed in the competing reactions, and the nitrogen fixation reaction presents a dominant position. The best-performing catalyst C8-Vo-TiO2 (Vo = oxygen vacancy) has a nitrogen fixation efficiency of up to 392 μmol·g·h−1.
Abstract
Ammonia is an important chemical raw material and non-carbon-based fuel. Photocatalytic ammonia production technology as a mild alternative to the traditional Harbor–Bosch route is carried out at the air, liquid, and solid three-phase interface. Promoting the activation of N2, depressing hydrogen evolution reaction (HER), and increasing the local N2 concentration around the catalyst surface are critical factors in achieving high conversion efficiency. In this paper, we proposed that defective TiO2 is surface-modified by alkyl acids with different carbon chain lengths (C2, C5, C8, C11, and C14) to tune the catalyst surface properties. The defect sites greatly promote N2 adsorption and activation. The wettability of the catalyst can be regulated from hydrophilic to hydrophobic by the length of the alkyl chain. The hydrophobic surface enhances the N2 adsorption and increases the local N2 concentration due to its aerophile. Meanwhile, it depresses the proton adsorption and HER. Overall, the nitrogen reduction reaction (NRR) is greatly promoted. Among the series of samples, they present a systematic change and have a maximal NRR performance for n-octanoic acid-defective TiO2 (C8-Vo-TiO2; Vo = oxygen vacancy). The rate of ammonia production can be as high as 392 μmol·g−1·h−1. This work provides a new strategy for efficient ammonia synthesis at the three-phase interface using photocatalyst technology.
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