Lee Seokhyun, Ha Heon Phil, Lee Jung-Hyun, Kim Jongsik
Extreme Materials Research Center, Korea Institute of Science and Technology, Seoul 02792, South Korea; Department of Chemical & Biological Engineering, Korea University, Seoul 02841, South Korea.
Extreme Materials Research Center, Korea Institute of Science and Technology, Seoul 02792, South Korea.
J Hazard Mater. 2023 Oct 15;460:132278. doi: 10.1016/j.jhazmat.2023.132278. Epub 2023 Aug 16.
NO rarely binds with labile oxygens of catalytic solids, whose Lewis acidic (LA) species possess higher binding strengths with NH (E) and HO than Brönsted acidic counterparts (BA-H; -OH), oftentimes leading to elevate energy barrier (E) and weaken HO tolerance, respectively. These limit NH-assisted wet NO reduction via Langmuir-Hinshelwood-type or Eley-Rideal (ER)-type model on LA species, while leaving ER-type analogue on BA-H species proper to reduce wet NO. Given hard-to-regulate strength/amount of -OH species and occasional association between E and E, NiVO (Ni) was rationally chosen as a platform to isolate mono-dentate SO/SO species for use as BA-H bonds via protonation to increase collision frequency (k') alongside with disclosure of advantages of SO/SO-functionalized NiVO (Ni-S) over Ni in reducing wet NO. Ni-S outperformed Ni in achieving a larger BA-H quantity (k'↑), increasing HO tolerance, and elevating oxygen mobility, thus promoting NO reduction activity/consequences under SO-excluding gases. VO-WO composite simulating a commercial catalyst could isolate mono-dentate SO/SO species and served as a control (VO-WO-S) for comparison. Ni-S was superior to VO-WO-S in evading ammonium (bi-)sulfate (AS/ABS) poison accumulation and expediting AS/ABS pyrolysis efficiency, thereby improving AS/ABS resistance under SO-including gases, while enhancing resistance against hydro-thermal aging.
NO很少与催化固体的不稳定氧结合，这些催化固体的路易斯酸性（LA）物种与NH（E）和HO的结合强度高于布朗斯特酸性对应物（BA-H；-OH），这通常分别导致能垒（E）升高和HO耐受性减弱。这些限制了通过LA物种上的朗缪尔-欣谢尔伍德型或埃利-里德耳（ER）型模型进行的NH辅助湿式NO还原，而BA-H物种上的ER型类似物则适合还原湿式NO。鉴于-OH物种的强度/数量难以调节以及E和E之间偶尔存在关联，合理选择NiVO（Ni）作为平台来分离单齿SO/SO物种，通过质子化用作BA-H键，以增加碰撞频率（k'），同时揭示SO/SO功能化的NiVO（Ni-S）在还原湿式NO方面优于Ni的优势。Ni-S在实现更大的BA-H数量（k'↑）、提高HO耐受性和提高氧迁移率方面优于Ni，从而在不含SO的气体下促进NO还原活性/结果。模拟商业催化剂的VO-WO复合材料可以分离单齿SO/SO物种，并用作对照（VO-WO-S）进行比较。Ni-S在避免硫酸铵（双）盐（AS/ABS）中毒积累和提高AS/ABS热解效率方面优于VO-WO-S，从而在含SO的气体下提高对AS/ABS的抗性，同时增强对水热老化的抗性。
