Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul, 02792, South Korea; Department of Chemical & Biological Engineering, Korea University, Seoul, 02841, South Korea.
Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul, 02792, South Korea; Department of Nano & Information Technology in Korea Institute of Science and Technology (KIST) School, University of Science and Technology (UST), Daejeon, 34113, South Korea.
J Hazard Mater. 2020 Jun 15;392:122347. doi: 10.1016/j.jhazmat.2020.122347. Epub 2020 Feb 18.
(Inverse) spinel-typed bimetallic sulfides are fascinating HO scissors because of the inclusion of S, which can regenerate metals (M, δ ≤ 2) used to produce OH via HO dissection. These sulfides, however, were under-explored regarding compositional, structural, and electronic tunabilities based on the proper selection of metal constituents. Motivated by S-modified Ni/Co promising to HO cleavage, NiCoS, NiCoS, NiS/CoS were synthesized and contrasted with regards to their catalytic traits. NiCoS provided the greatest activity in dissecting HO among the catalysts. Nonetheless, NiCoS catalyzed HO scission primarily via homogeneous catalysis mediated by leached Ni/Co. Conversely, NiCoS, NiS, and CoS catalyzed HO cleavage mainly via unleached Ni/Co-enabled heterogeneous catalysis. Of significance, NiCoS provided Lewis acidic strength favorable to adsorb HO and desorb OH compared to NiS and CoS, respectively. Of additional significance, NiCoS provided S with lesser energy required to reduce M via e- transfer than NiS/CoS. Hence, NiCoS prompted HO scission cycle per unit time better than NiS/CoS, as evidenced by kinetic assessments. NiCoS was also superior to NiCoS because of the elongated lifespan anticipated as OH producer, resulting from heterogeneous catalysis with moderate Ni/Co leaching. Furthermore, NiCoS revealed the greatest recyclability and mineralization efficiency in decomposing recalcitrants via OH-mediated oxidation.
（反）尖晶石型双金属硫化物因其包含 S 而成为引人注目的 HO 剪刀，S 可以通过 HO 分解来再生用于产生 OH 的金属（M，δ ≤ 2）。然而，这些硫化物在组成、结构和电子可调性方面的研究还不够充分，这是基于对金属成分的适当选择。受 S 改性的 Ni/Co 有望促进 HO 裂解的启发，合成了 NiCoS、NiCoS 和 NiS/CoS，并对它们的催化特性进行了对比。在这些催化剂中，NiCoS 在分解 HO 方面表现出最高的活性。然而，NiCoS 主要通过浸出的 Ni/Co 介导的均相催化来催化 HO 的断裂。相反，NiCoS、NiS 和 CoS 主要通过未浸出的 Ni/Co 实现的多相催化来催化 HO 的断裂。值得注意的是，与 NiS 和 CoS 相比，NiCoS 提供了有利于吸附 HO 和脱附 OH 的路易斯酸性强度。此外，与 NiS/CoS 相比，NiCoS 提供了通过电子转移还原 M 所需的较低能量。因此，NiCoS 比 NiS/CoS 更能促进单位时间内的 HO 断裂循环，这可以通过动力学评估来证明。由于 NiCoS 具有适度的 Ni/Co 浸出的多相催化，因此作为 OH 产生剂的预期寿命更长，因此也优于 NiCoS。此外，NiCoS 在通过 OH 介导的氧化分解难降解污染物方面表现出最大的可回收性和矿化效率。
