Metal and bimetal doped TiO₂ supported on CNT hybrids were successfully synthesized in supercritical CO₂ medium and evaluated for their solar light photocatalytic efficiency to degrade the endocrine disruptors clothianidin, estrone and estradiol. Metallic dopants analyzed were Pd and Cu at metal concentrations of 2% by weight. The morphological analysis of the hybrids showed metal-doped TiO₂ nanoparticles of around 10 nm over CNT. All of them exhibited highly crystalline anatase phase and shifted the absorption edge through the visible region. Band gap reduction was more pronounced for bimetallic Pd, Cu codoped TiO₂ (TiO₂/CNT/Pd-Cu) than with monometal-doped samples (TiO₂/CNT/Pd and TiO₂/CNT/Cu). Bimetalic codoping also led to an enhancement in the charge transfer process (Rct=1.4 ohms and Rs=19.4 ohms for TiO₂/CNT/Pd-Cu vs. Rct=13.0 ohms and Rs=38.5 ohms for TiO₂/CNT) and photodegradation of target endocrine disruptors. At the vanishing times of these pollutants by treatment with TiO₂/CNT/Pd-Cu, the removals achieved with the metal-doped catalyst least active (TiO₂/CNT/Cu) were 80% (clothianidin), 84% (estrone) and 82% (estradiol), far higher than those observed with commercial P25 (53% for clothianidin, 56% for estrone and 54% for estradiol). The improved performance of bimetallic TiO₂/CNT/Pd-Cu over its monometallic references was explained on the basis of a combination of factors mainly related to its band gap structure, easier availability of charge carriers and plasmonic effects. Furthermore, this catalyst showed a highly stable photocatalytic performance. Thus, neither background species present in a real WWTP effluent, nor four successive uses of the catalyst significantly affected to the removal efficiency of pollutants.

_{在超临界CO 2}介质中成功合成了负载在CNT杂化物上的金属和双金属掺杂的TiO ₂ ，并评估了它们在太阳能光催化降解内分泌干扰物噻虫胺、雌酮和雌二醇的效率。分析的金属掺杂剂是金属浓度为 2%（重量）的 Pd 和 Cu。杂化物的形态分析显示金属掺杂的TiO ₂纳米颗粒在CNT上约10nm。它们都表现出高度结晶的锐钛矿相，并且吸收边缘通过可见区域移动。双金属 Pd、Cu 共掺杂 TiO ₂ (TiO ₂ /CNT/Pd-Cu) 的带隙减小比单金属掺杂样品 (TiO ₂ /CNT/Pd 和 TiO ₂ /CNT/Cu)。双金属共掺杂还增强了电荷转移过程（TiO _{2 /CNT/Pd-Cu 的 Rct=1.4 ohms 和 Rs=19.4 ohms 对比 TiO 2} /CNT 的 Rct=13.0 ohms 和 Rs=38.5 ohms ）和光降解目标内分泌干扰物。在这些污染物通过用 TiO ₂ /CNT/Pd-Cu 处理消失时，使用最低活性的金属掺杂催化剂 (TiO ₂ /CNT/Cu) 实现的去除率为 80%（噻虫胺）、84%（雌酮）和 82%（雌二醇），远高于用商业 P25 观察到的结果（噻虫胺 53%，雌酮 56%，雌二醇 54%）。双金属TiO _{2的改进性能}/CNT/Pd-Cu 对其单金属参考的解释是基于主要与其带隙结构、更容易获得电荷载流子和等离子体效应相关的因素的组合。此外，该催化剂显示出高度稳定的光催化性能。因此，实际 WWTP 流出物中存在的背景物质和催化剂的四次连续使用都不会显着影响污染物的去除效率。