四溴双酚A(Tetrabromobisphenol A，TBBPA)作为应用最广泛的一类溴代阻燃剂(brominated flame retardants, BFRs)，由于其独特的性质和较低的成本，已被广泛应用于多个行业而存在于多种环境介质中。同时由于其潜在的环境危害，针对该类物质环境行为的研究也逐渐成为了人们关注的热点。本文以水体中TBBPA为目标污染物，考察其在氙(Xe)灯作为光源的模拟太阳光照射下的光化学转化行为和机理。研究表明，水体中TBBPA在Xe灯作为光源的模拟太阳光下的直接光化学行为符合准一级反应动力学方程。随着TBBPA的浓度从0.1 mg/L到10 mg/L，其反应速率常数k由2.80 × 10-2降低到0.70 × 10-2 min-1，表明该过程受传质速率的影响较大。将溶液中腐殖酸(humic acid，HA)的浓度由0提高至100 mg/L，其光解速率常数由2.53 × 10-2降低到0.39 × 10-2 min-1，造成该现象的主要原因是HA与TBBPA分子之间存在对光子的竞争吸附，导致TBBPA的光解速率减慢。中性条件下，TBBPA在Xe灯模拟的自然光照条件下的光化学降解速率最快。采用电子自旋共振(Electron spin resonance，ESR)和活性氧自由基淬灭实验进行自由基的测定，结果表明TBBPA的光降解过程中存在活性氧自由基(•OH，•O2-，1O2)的氧化过程，同时该过程受超氧阴离子(•O2-)的影响最大。光照180 min后，TOC去除率为35.0%，而TBBPA的去除率高达99.1%。光解过程中产生的中间产物主要包括溴离子、双酚A、2,6-二溴苯酚、2-溴苯酚、苯酚等，表明TBBPA在模拟太阳光条件下的光转化途径主要包括了脱溴过程和碳碳键的断裂。同时，本研究采用水热合成法制备出可见光催化剂氧化铋，并在此基础上对其进行石墨烯掺杂改性。结果表明，随着石墨烯掺杂量的提高(0-5%)，催化剂的片层结构明显，空隙变大；同时光吸收能力增强。但ESR检测结果中没有明显检测到三种活性氧自由基，推测原因可能是该催化剂在特定波长532 nm下没有被激发，同时可能由于该过程产生的自由基量低于仪器检出限。以TBBPA为目标污染物，研究其在可见光(λ > 420 nm)照射条件下的光催化降解行为，所采用的反应体系为0.01 M NaOH溶液(pH = 12)。结果表明，掺杂石墨烯的光催化剂在一定程度上促进了TBBPA的光催化降解行为，主要原因是由于石墨烯具有很强的电子存储能力，石墨烯独特的结构特征使其能够有效捕获反应过程中产生的电子，由于电子被捕获而导致光生电子(e-)和空穴(h+)的复合率大大降低，提高光催化效率。TBBPA的光催化降解过程同样符合准一级反应动力学方程。光解速率随TBBPA浓度的升高而降低；HA作为一种光敏化剂，在光照条件下产生了多种活性基团，从而促进了光催化行为的进行；自由基淬灭实验中采用KI，NaN3和1,4-对苯醌作为•OH，1O2和•O2-的淬灭剂，结果表明，1,4-对苯醌对TBBPA的光催化行为抑制作用最为明显，该结论与直接光解实验中结果一致。

As one of the most important brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA) has been widely used in many industries and has been detected in various environmental matrices because of its properties and low cost. Due to its potential environmental hazards, the environmental behaviors of TBBPA have been the research hotpots. In this paper, TBBPA was chosen as the model pollutant in water and the photochemical transformation under Xenon lamp was investigated. A systematic study on direct photolysis of TBBPA in water was investigated under simulated sunlight irradiation. The results showed that the photolysis of TBBPA followed apparent pseudo-first-order kinetics. The photolysis rate constants (k) changed from 2.80 × 10-2 to 0.70 × 10-2 min-1 with the concentrations of TBBPA varying from 0.1 to 10 mg/L. Increasing humic acid (HA) concentration from 0-100 mg/L led to the decrease of k from 2.53 × 10-2 to 0.39 × 10-2 min-1, which was due to the competitive adsorption for photons between HA and TBBPA molecules. The photolysis rate was faster at near-neutral conditions (pH = 6 and 7) than that in either acidic or basic conditions. Electron spin resonance (ESR) and reactive oxygen species (ROS) scavenging experiments indicated that TBBPA underwent self-sensitized photo oxidation via ROS (•OH, 1O2 and •O2-), and the process was mainly controlled by •O2-. After irradiation of 180 min, about 35.0% reduction of TOC occurred accompanied with approximate 99.1% of TBBPA removed, indicating the formation of intermediates. The detection of products (i.e. Br-, bisphenol A (BPA), 2,6-dibromophenol, 2-bromophenol, phenol) revealed that the main photolytic pathways of TBBPA were debromination and broken of C-C bond.Meanwhile, the study prepared bismuth oxide (Bi2O3) and graphene doped Bi2O3 by hydrothermal synthesis. The catalysts were characterized and the results showed that with the increasing amount of graphene doping (0-5%), the lamellar structure of the catalyst significantly heightened, the gaps in the catalyst became larger and the optical absorption capability enhanced. However, there were no significant signals of ROS detected in ESR, presumably due to the catalyst could not be excited at a particular wavelength of 532 nm and the amount of free radicals produced in the process was too low to be detected.TBBPA was chosen as the target pollutant to test the photocatalysis activity of two catalysts. The reaction system was prepared with 0.01 M NaOH solution and all the experiments were conducted under visible light (λ > 420 nm) conditions. The scavenging experiments were performed using potassium iodide (KI), sodium azide (NaN3) and 1,4-benzoquinone. The results showed that the graphene doped Bi2O3 could promote the photocatalytic degradation of TBBPA. Graphene has a great storage capacity for electrons, decreasing the recombination of photogenerated electrons and holes. Photocatalytic degradation of TBBPA under λ > 420 nm also followed apparent pseudo-first-order kinetics. The photocatalysis rate constants (k) decreased with increasing concentrations of TBBPA; HA could produce a variety of active groups as a photosensitizing agent in the light conditions, thereby promoting the photocatalysis behavior of TBBPA; ROS scavenging experiments indicated that the inhibition caused by 1,4-benzoquinone was most obvious, which was consistent with the results in the direct photolysis experiments.