Catalysts
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2021
·Vol. 11
·期 5
·543
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IF 4.146
Zechen Liang,Mingkai Zhang,Sai Zhang,Yongquan Qu
Selective hydrogenation of halonitrobenzenes into haloanilines represents a green process to replace the environmentally unfriendly non-catalytic chemical reduction process in industry. However, this transformation often suffers from serious dehalogenation due to the easy break of carbon-halogen bonds on metal surfaces. Modulations of the electronic structure of the supported Pd nanoparticles on Lewis-basic layered double hydroxides have been demonstrated to promote catalytic activity and selectivity for hydrogenation of halonitrobenzenes into haloanilines. Mechanism studies suggest that Pd with the enhanced electron density not only improves the capability for hydrogen activation, but also generates the partially negative-charged hydrogen species to suppress the electrophilic attack on the carbon-halogen bond and avoid the dehalogenation.Keywords:Pd nanoparticles;hydrogenation;halonitrobenzenes;haloanilines
研究领域:
化学
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
ANALYST
·
2016
·Vol. 141
·期 7
·2303-2307
·
IF 4.033
Lina Yao,Fei Yan,Bin Su
Halonitrobenzenes (HNBs) are a class of molecules that are highly toxic to human health and the ecological environment. Thus, effective and efficient approaches capable of monitoring and detecting HNBs are greatly desired. We report herein a simple and sensitive method for the detection of HNBs. The detection was based on the indium tin oxide (ITO) electrodes modified with a binary assembly of highly ordered surfactant micelles (OSMs) and silica mesochannels (SMs). The SMs have a diameter of 2–3 nm and a vertical orientation, which provide a hard support to stabilize soft OSMs. Moreover, each OSM consists of a hydrophobic core due to the organized assembly of surfactant hydrocarbon chains, which can selectively extract and concentrate lipophilic HNBs from aqueous media, allow their transport to the underlying ITO electrode surface and therein their detection by voltammetry. As a proof-of-concept experiment, 1-chloro-3-nitrobenzene, 1-chloro-4-nitrobenzene, 1-bromo-4-nitrobenzene and 2,4-dinitrobromobenzene were analyzed in aqueous solutions. A simple and fast detection was achieved in all cases, with a wide linear dynamic range, a high sensitivity and a low limit of detection at the ppb level. Apart from the extraction ability, the OSMs also prohibited the access of and surface contamination by unwanted substances, showing excellent anti-fouling and anti-interference power. Indeed, as we demonstrated, the sensor could be employed for direct electrochemical detection of HNBs in complex samples, such as lake water and soil dispersion, without any pre-treatment, indicating its potential usefulness in practical analysis.
研究领域:
环境科学
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分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Hongbo Yu,Shuibo Wang,Lin Zhu,Chunzheng Wu
Pt nanocatalysts exhibits superior activity towards the hydrogenation reaction of halonitrobenzenes (HNBs), but the selectivity to the valuable product haloanilines (HANs) is always poor due to the unavoidable dehalogenation process. In this study, we find that coating a thin Sn layer on Pt nanoparticles (NPs) could improve not only the hydrogenation activity but also the selectivity to HANs. These core–shell structured Pt@Sn NPs with different Sn shell thickness were synthesized by one-pot reduction, and their catalytic performance in the hydrogenation reaction of p -chloronitrobenzene to p -chloroaniline could be effectively regulated by the Pt/Sn ratio. The catalyst with a Pt/Sn ratio of 5/1 achieved the highest p -chloronitrobenzene conversion (96.5 %) and excellent selectivity to p -chloroaniline (97.9 %). The kinetic study and H 2 -TPD analysis indicated that the Sn species on Pt could facilitate the adsorption of p -chloronitrobenzene and the dissociation of H 2 . The designed Pt@Sn core–shell nanocatalysts are applicable to a wide range of hydrogenation reactions.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2021
·
IF 5.455
Wei Wu,Wei Zhang,Yu Long,Jiaheng Qin,Jiantai Ma
Carbon material derived from certain MOF usually still has plenty of microporous structures, the mass transfer process is severely limited. In this work, in the assistance of dicyandiamide, nitrogen doped carbon confined atomically dispersed Fe species (Fe–N–C) with interconnected mesoporous pores by a facile one-step pyrolysis process of Fe-doped zeolitic imidazolate framework (Fe-doped ZIF) is prepared. Through simply adjusting the amount of dicyandiamide added, Fe–N–C with various morphologies, pore structures and chemical compositions could be obtained. The specific surface area of the materials increases first and then decreases with the increase content of dicyandiamide, and the pore structure also changes accordingly. Fe–N–C possesses the largest specific surface area with interconnected pore structure when the mass ratio of dicyandiamide to Fe-doped ZIF reaches 1:1 (Fe–N–C–1). And Fe–N–C–1 shows the optimal catalytic activity compared with other catalysts for the transfer hydrogenation of halonitrobenzenes. Moreover, the Fe–N–C–1 exhibits good stability and could be reused without obvious decrease of catalytic activity. This work may afford certain thought for rationally designing high-performance catalysts derived from MOF .
研究领域:
材料科学
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催化化学
✓ 已验证
DOI
高影响因子
ACS Applied Nano Materials
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2022
·
IF 6.14
Fan Yang,Hongbo Yu,Chunzheng Wu,Shiwei Wang,Tong Li,Hongfeng Yin
Supported Rh nanoparticles (NPs) exhibit excellent activity for the chemoselective hydrogenation of halonitrobenzenes (HNBs), but their selectivity to aromatic amines is not satisfactory due to the side reaction on the carbon–halogen bonds, and their recycling stability is limited due to the aggregation and the leaching of active component during the long-term usage. Herein, we design a yolk–shell-structured catalyst that consists of RhCu alloy cores and hollow/microporous carbon shells (HCS) to overcome these problems. The obtained RhCu@HCS catalyst with a Rh/Cu ratio of 1:1 showed good activity, selectivity, and stability in the hydrogenation of p-CNB (p-chloronitrobenzene) to produce p-CAN (p-chloroaniline) due to the synergistic effect between Rh and Cu. The protective carbon shells not only prevented the aggregation of metal NPs but also allowed the reactants to diffuse freely across the shells. Therefore, our research provides a general strategy to design highly efficient and stable hydrogenation catalysts.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Surfaces and Interfaces
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2024
·
IF 5.7
Xusheng Yang,Le Zhou,Changsong Chen,Weidong Jiang,Xiaobin Zhang,Pingchuan Pan,Shengbin Zhou,Kaiming Zhang,Bin Xu
Novel magneto-thermo dual responsive organic-inorganic hybrid materials (PdCu/Fe 3 O 4 @SiO 2 @PNIPAM) were successfully prepared under γ-ray irradiation in this work. The γ-ray irradiation simultaneously induced the grafting of the polymer PNIPAM, and the in-situ anchoring of metallic Pd and Cu via an irradiation reduction. The catalytic performance of the prepared PdCu/Fe 3 O 4 @SiO 2 @PNIPAM hybrid material ( abbr . PdCu/FSP) was investigated for the dehydrogenation of ammonia borane (AB) and the tandem hydrogenation of halonitrobenzenes. The results showed that the as-prepared PdCu/FSP exhibited more excellent catalytic performance in the tandem hydrogenation reaction of halonitrobenzenes in comparison with a controlled sample by a traditional preparation method. Furthermore, the PdCu/FSP catalyst prepared at a radiation dose of 25 kGy achieved excess 99 % yield of m-chloroaniline (m-CAN) at room temperature within 5 min. The PdCu/FSP hybrid material could be easily recycled by simple magnetic separation, and increasing temperature led to obvious time-shortening behavior for facile magnetic separation. Owing to lack of the intrinsic drawbacks of conventional chemical reductants and radical initiators, the gamma-ray irradiation method provides an available strategy for the construction of hybrid catalytic materials towards the hydrogenated reduction of halonitrobenzenes.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
WATER RESEARCH
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2022
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IF 13.4
Shaoyang Hu,Han Yeong Kaw,Lizhong Zhu,Wei Wang
Halogenated aromatic disinfection byproducts (DBPs) exhibited similar total organic halogen levels in chlorinated drinking water samples as compared with aliphatic ones, and they predominantly accounted for the overall toxicity of the samples. Among the reported halogenated aromatic DBPs, halonitrophenols (HNPs) have received particular attention in recent years due to the relatively high risk in drinking water. In this study, a new group of halogenated aromatic DBPs were detected and then proposed to be halohydroxybenzonitriles (HHBNs) by employing the ultra-performance liquid chromatography/tandem mass spectrometers. Thereafter, the specific HHBN species in drinking water were theoretically speculated and then thoroughly identified with standard compounds. Their occurrence in drinking water was investigated, their cytotoxicity was evaluated, and their stability in the presence of chlorine was assessed. Seven newly identified HHBNs, including 3,5-dichloro-4-hydroxybenzonitrile, 3,5-dichloro-2-hydroxybenzonitrile, 5-bromo-3-chloro-4-hydroxybenzonitrile, 5-bromo-3-chloro-2-hydroxybenzonitrile, 3,5-dibromo-4-hydroxybenzonitrile, 3,5-dibromo-2-hydroxybenzonitrile, and 3,5-diiodo-4-hydroxybenzonitrile, showed 100% detection frequency in the collected drinking water samples with concentrations up to 36 ng/L. HHBNs exhibited significantly higher cytotoxicity in Chinese hamster ovary cells than regulated DBPs (e.g., trihalomethanes and haloacetic acids), which might be contributed by their cellular uptake efficiency and nucleophilicity. The seven HHBNs were proved to undergo transformation during chlorination following pseudo-first-order decay with half-lives in the range of 9–63 h. More importantly, in comparison to HNPs, which showed relatively high toxicity and strong stability among the halogenated aromatic DBPs, HHBNs presented comparable concentration-cytotoxicity contribution (50%) and slightly weaker stability (43%), suggesting that HHBNs should be a new group of DBPs of concern in drinking water.
研究领域:
环境科学
·
毒理学
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公共卫生
✓ 已验证
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2019
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IF 6.97
Chunshan Lu,Qianwen Zhu,Xuejie Zhang,Haoke Ji,Yebin Zhou,Hao Wang,Qiangqiang Liu,Juanjuan Nie,Wenfeng Han,Xiaonian Li
Achieving high selectivity is one of the major challenges for the noble metal catalysts. A strategy of decoration of Pd nanoparticles by N–S doped carbon quantum dots (N,S-CQDs) to regulate selectivity is proposed. Through adjusting the loading amounts of N,S-CQDs, high selectivity toward catalytic hydrogenation reactions can be obtained. N,S-CQDs facilely adhere to the Pd nanoparticle via surface reactions among C–S/C–N species of N,S-CQDs and C–O species of the carbon support under the catalysis of Pd particles. N loss was detected due to the transformation of some C–N species into nitrogen-containing soluble substances or gas. However, S-containing species, specially −SO2/SO3 species, are turned into C–S–C (thiophene-S), leading to a strong coordination between Pd and S. As a result, a N,S-CQDs-Pd interface is fabricated, in which electrons transfer from Pd to S species and the interface of Pd–S plays a major role in hydrogen spillover and generation of dissociated hydrogen with negative charge. Consequently, Pd@N,S-CQDs suppress the hydrodehalogenation and exhibit superior conversion and selectivity (both 100%) for the selective hydrogenation of various halonitrobenzenes. N,S-CQDs as a nonmetallic promoter of metal catalysts provides a promising strategy for the improvement of selectivity.
研究领域:
化学
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材料科学
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催化
✓ 已验证
DOI
高影响因子
Nature Catalysis
·
2021
·Vol. 4
·期 10
·840-849
·
IF 41.813
Guan Qiaoqiao,Zhu Chuwei,Lin Yue,Vovk Evgeny I.,Zhou Xiaohong,Yang Yong,Yu Hancheng,Cao Lina,Wang Hengwei,Zhang Xiaohui,Liu Xinyu,Zhang Mengkai,Wei Shiqiang,Li Wei-Xue,Lu Junling
Particle size governs the geometric and electronic structure of metal nanoparticles (NPs), shaping their catalytic performance. However, size-dependent entanglement in the geometric and electronic structures often leads to a trade-off between activity and selectivity, limiting the optimization of the overall catalytic performance. Here we show that precisely controlled deposition of a platinum monolayer on large gold NPs breaks the activity–selectivity trade-off on particle size in platinum-catalysed chemoselective hydrogenation of halonitrobenzenes, resulting in a remarkable activity, along with a 99% selectivity for haloanilines under mild conditions. The high activity results from upshift of the platinum 5 d -band centre through platinum lattice expansion and ligand effect, whereas the high selectivity is caused by exposing more terrace sites on large particles. The geometric and electronic properties of bimetallic monolayer materials, distinct from monometallic NPs and alloys, constitute a promising platform for the rational design of metal catalysts with superior performance in hydrogenation reactions.
研究领域:
催化
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材料科学
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化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）