{"title":"以原始海相粘土为催化剂超高效还原 4-硝基苯酚","authors":"Peiping Zhang, Tongtong Liu, Xue Sun, Qing Liang, Wei Zhang, Weikun Ning, Wenqing Li, Xuefa Shi, Shiding Miao","doi":"10.1007/s42860-023-00266-0","DOIUrl":null,"url":null,"abstract":"<p>Natural clays are often employed as substrates for heterogeneous catalysts. However, the direct use of raw clays as catalysts has received less research attention. The objective of the present study was to help fill this gap by investigating catalytic properties of raw pelagic clays (PC) collected from the Indian Ocean. The raw PC were discovered to be efficient catalysts in the reduction of 4-nitrophenol (4-NP) in the presence of NaBH<sub>4</sub>. The effects of parameters including pH values, dosages of PC, and initial concentration of 4-NP and NaBH<sub>4</sub> on the conversion or degradation rate of 4-NP have been investigated. The 4-NP was observed to be completely degraded within 480 s under conditions of 0.10 mM 4-NP, 25.0 mM NaBH<sub>4</sub>, and 0.20 g/L PC at an initial pH value of 7.0. The apparent rate constant was evaluated to be 27.53 × 10<sup>–3</sup> s<sup>–1</sup>. Unlike previous pseudo-first order kinetics experiments, the induction period and degradation stages were observed to occur simultaneously during the PC catalysis. The S-shaped kinetics for 4-NP conversion was found to be perfectly matched by Fermi's function, and the enzyme-like catalysis by PC was appointed to describe the kinetics. Species of Fe(III), Mn(IV), and Mn(III) in PC were found to be essential, and were partly reduced to Fe(0) and Mn(II) by NaBH<sub>4</sub> in our reaction, contributing to rapid conversion of 4-NP to 4-aminophenol (4-AP). The raw PC was converted to magnetic PC (m-PC) particles, which made PC particles separate easily for cycling use. This discovery would also have applications in continuous flow-fluid catalysis.</p>","PeriodicalId":10320,"journal":{"name":"Clays and Clay Minerals","volume":"13 1","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2023-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Super-efficient Reduction of 4-nitrophenol Using Raw Pelagic Clays as Catalysts\",\"authors\":\"Peiping Zhang, Tongtong Liu, Xue Sun, Qing Liang, Wei Zhang, Weikun Ning, Wenqing Li, Xuefa Shi, Shiding Miao\",\"doi\":\"10.1007/s42860-023-00266-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Natural clays are often employed as substrates for heterogeneous catalysts. However, the direct use of raw clays as catalysts has received less research attention. The objective of the present study was to help fill this gap by investigating catalytic properties of raw pelagic clays (PC) collected from the Indian Ocean. The raw PC were discovered to be efficient catalysts in the reduction of 4-nitrophenol (4-NP) in the presence of NaBH<sub>4</sub>. The effects of parameters including pH values, dosages of PC, and initial concentration of 4-NP and NaBH<sub>4</sub> on the conversion or degradation rate of 4-NP have been investigated. The 4-NP was observed to be completely degraded within 480 s under conditions of 0.10 mM 4-NP, 25.0 mM NaBH<sub>4</sub>, and 0.20 g/L PC at an initial pH value of 7.0. The apparent rate constant was evaluated to be 27.53 × 10<sup>–3</sup> s<sup>–1</sup>. Unlike previous pseudo-first order kinetics experiments, the induction period and degradation stages were observed to occur simultaneously during the PC catalysis. The S-shaped kinetics for 4-NP conversion was found to be perfectly matched by Fermi's function, and the enzyme-like catalysis by PC was appointed to describe the kinetics. Species of Fe(III), Mn(IV), and Mn(III) in PC were found to be essential, and were partly reduced to Fe(0) and Mn(II) by NaBH<sub>4</sub> in our reaction, contributing to rapid conversion of 4-NP to 4-aminophenol (4-AP). The raw PC was converted to magnetic PC (m-PC) particles, which made PC particles separate easily for cycling use. 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引用次数: 0
摘要
天然粘土经常被用作异相催化剂的底物。然而,直接使用未加工粘土作为催化剂的研究较少受到关注。本研究的目的是通过研究从印度洋采集的原始浮游粘土(PC)的催化特性来填补这一空白。研究发现,在 NaBH4 的存在下,原始浮游黏土是还原 4-硝基苯酚(4-NP)的高效催化剂。研究了 pH 值、PC 用量、4-NP 和 NaBH4 的初始浓度等参数对 4-NP 转化或降解率的影响。在 0.10 mM 4-NP、25.0 mM NaBH4 和 0.20 g/L PC(初始 pH 值为 7.0)的条件下,4-NP 在 480 秒内完全降解。表观速率常数为 27.53 × 10-3 s-1。与以往的伪一阶动力学实验不同,在 PC 催化过程中,诱导期和降解期同时发生。4-NP 转化的 S 型动力学与费米函数完全吻合,并认为 PC 的酶催化作用可以描述该动力学。研究发现 PC 中的铁(III)、锰(IV)和锰(III)物种是必不可少的,它们在我们的反应中被 NaBH4 部分还原为铁(0)和锰(II),从而促使 4-NP 快速转化为 4-氨基苯酚(4-AP)。未加工的 PC 被转化为磁性 PC(m-PC)颗粒,使 PC 颗粒易于分离,可循环使用。这一发现还将应用于连续流流体催化。
Super-efficient Reduction of 4-nitrophenol Using Raw Pelagic Clays as Catalysts
Natural clays are often employed as substrates for heterogeneous catalysts. However, the direct use of raw clays as catalysts has received less research attention. The objective of the present study was to help fill this gap by investigating catalytic properties of raw pelagic clays (PC) collected from the Indian Ocean. The raw PC were discovered to be efficient catalysts in the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4. The effects of parameters including pH values, dosages of PC, and initial concentration of 4-NP and NaBH4 on the conversion or degradation rate of 4-NP have been investigated. The 4-NP was observed to be completely degraded within 480 s under conditions of 0.10 mM 4-NP, 25.0 mM NaBH4, and 0.20 g/L PC at an initial pH value of 7.0. The apparent rate constant was evaluated to be 27.53 × 10–3 s–1. Unlike previous pseudo-first order kinetics experiments, the induction period and degradation stages were observed to occur simultaneously during the PC catalysis. The S-shaped kinetics for 4-NP conversion was found to be perfectly matched by Fermi's function, and the enzyme-like catalysis by PC was appointed to describe the kinetics. Species of Fe(III), Mn(IV), and Mn(III) in PC were found to be essential, and were partly reduced to Fe(0) and Mn(II) by NaBH4 in our reaction, contributing to rapid conversion of 4-NP to 4-aminophenol (4-AP). The raw PC was converted to magnetic PC (m-PC) particles, which made PC particles separate easily for cycling use. This discovery would also have applications in continuous flow-fluid catalysis.
期刊介绍:
Clays and Clay Minerals aims to present the latest advances in research and technology concerning clays and other fine-grained minerals, including but not limited to areas in agronomy, ceramics, colloid chemistry, crystallography, environmental science, foundry engineering, geochemistry, geology, medicinal chemistry, mineralogy, nanoscience, petroleum engineering, physical chemistry, sedimentology, soil mechanics, and soil science. Clays and Clay Minerals exists to disseminate to its worldwide readership the most recent developments in all of these aspects of clay materials. Manuscripts are welcome from all countries.