Department of Chemical Engineering , University of Illinois at Chicago , 810 S. Clinton St. , Chicago , Illinois 60607 , United States.
Department of Mechanical and Industrial Engineering , University of Illinois at Chicago , 842 W. Taylor St. , Chicago , Illinois 60607 , United States.
Environ Sci Technol. 2018 Nov 6;52(21):12675-12684. doi: 10.1021/acs.est.8b04103. Epub 2018 Oct 11.
This research focused on improving mineralization rates during the advanced electrochemical oxidation treatment of agricultural water contaminants. For the first time, bismuth-doped tin oxide (BDTO) catalysts were deposited on Magnéli phase (Ti O, n = 4-6) reactive electrochemical membranes (REMs). Terephthalic acid (TA) was used as a OH probe, whereas atrazine (ATZ) and clothianidin (CDN) were chosen as model agricultural water contaminants. The BDTO-deposited REMs (REM/BDTO) showed higher compound removal than the REM, due to enhanced OH production. At 3.5 V/SHE, complete mineralization of TA, ATZ, and CDN was achieved for the REM/BDTO upon a single pass in the reactor (residence time ∼3.6 s). Energy consumption for REM/BDTO was as much as 31-fold lower than the REM, with minimal values per log removal of <0.53 kWh m for TA (3.5 V/SHE), <0.42 kWh m for ATZ (3.0 V/SHE), and 0.83 kWh m for CDN (3.0 V/SHE). Density functional theory simulations provided potential dependent activation energy profiles for ATZ, CDN, and various oxidation products. Efficient mass transfer and a reaction mechanism involving direct electron transfer and reaction with OH were responsible for the rapid and complete mineralization of ATZ and CDN at very short residence times.
本研究专注于提高农业水污染先进电化学氧化处理过程中的矿化速率。首次将掺铋氧化锡（BDTO）催化剂沉积在 Magnéli 相（Ti O，n = 4-6）反应性电化学膜（REMs）上。对苯二甲酸（TA）被用作 OH 探针，而莠去津（ATZ）和噻虫啉（CDN）被选为农业水污染的模型化合物。BDTO 沉积的 REMs（REM/BDTO）比 REM 显示出更高的化合物去除率，因为它增强了 OH 的产生。在 3.5 V/SHE 下，在反应器中单次通过（停留时间约 3.6 s）即可完全矿化 TA、ATZ 和 CDN。与 REM 相比，REM/BDTO 的能耗降低了 31 倍，每对数去除的能量消耗最小，TA（3.5 V/SHE）为 <0.53 kWh m，ATZ（3.0 V/SHE）为 <0.42 kWh m，CDN（3.0 V/SHE）为 0.83 kWh m。密度泛函理论模拟提供了 ATZ、CDN 和各种氧化产物的电位相关的活化能曲线。高效的传质和涉及直接电子转移和与 OH 反应的反应机制是在极短的停留时间内实现 ATZ 和 CDN 快速和完全矿化的原因。
