FUEL
·
2025
·
IF 7.5
Ruotong Cui,Wenlong Xu,Yanpeng Zhang,Jingxian Wang,Yingyun Qiao,Yuanyu Tian
Identifying and analyzing the reaction process of S atoms in coal at the molecular level has been a key and difficult problem in coal chemistry. Here, we used dibenzyl sulfide as a model compound for S-containing substances in coal and predicted the pyrolysis process of C-S in coal through the pyrolysis products, which indicated that the C-S bond would be broken firstly above the energetic basis point to generate intermediate S-containing radicals. A hydrogen-donating solvent (9, 10-dihydroanthracene) was utilized as the radical trapping agent to reveal the S-containing radical reaction process through the changes of the products before and after the trapping reaction. Density functional theory was further used to calculate the pyrolysis process to help verify the radical history of the response. Finally, pyrolysis experiments were performed on raw coal to confirm the generality of the pyrolytic radical regulatory mechanism of C-S. This study identifies and analyzes the relationship between C-S structure and reactivity during coal pyrolysis at the molecular level, and confirms the universal law of raw coal’s pyrolytic radical reaction mechanism. This not only provides theoretical guidance and a basis for the free radical regulation process during the pyrolysis of S-containing structures in coal but also provides theoretical support for the clean and efficient utilization of coal.
研究领域:
煤炭化学
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Hongyu Niu,Xing-Bao Wang,Jingjie Luo,Jiaxin Liu,Chuang Li,Wen-Ying Li,Changhai Liang
Desulfurization plays a critical role in refining crude oil to produce fuel and the manufacture of fine chemicals. However, its low efficiency becomes a great challenge for the present desulfurization if only the C-S cleavage is considered a promising approach to reducing hydrogen consumption under atmospheric pressure. Accordingly, we investigate the critical factors necessary to achieve high C-S cleavage of dibenzothiophenes under mild conditions of 0.1 MPa and H 2 /oil = 100. The mechanism of reactive adsorption desulfurization of dibenzothiophenes with or without steric hindrance at atmospheric pressure on Pt/ZnO is proposed by studying the adsorption model of active metal sites, the Pt efficiency in C-S cleavage influenced by the steric hindrance and the structural evolution of Pt active centers in the presence of sulfur adsorption/deposition. Based on both experimental and DFT results, we report C-S cleavage of dibenzothiophenes with (TOF = 15 h −1 ) or without steric hindrance (TOF = 128 h −1 ) that can be highly efficiently fractured (99.9%) by the interface between PtS x and ZnO . This work has great practical significance for developing atmospheric industrial adsorbents for ultra-deep reactive adsorption desulfurization.
研究领域:
化学工程
·
催化材料
·
能源化工
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2017
·
IF 4.849
Qiujie Tang,Zhaogang Bian,Wei Wu,Jin Wang,Ping Xie,Charles U. Pittman,Jr.,Aihua Zhou
The method for constructing C–S bonds is very important in organic synthesis. Here a new sulfenylation method to generate flavone thioether derivatives was developed by employing aromatic or alkyl halides, S powder and Na2S2O3 as reactants. Good yields of regioselective Calkyl–S and Caryl–S-substituted flavones were generated under relatively environmentally friendly and simple conditions. This method might be potentially applicable to large scale production, and it enriches current sulfenylation methods.
研究领域:
有机化学
·
药物合成
✓ 已验证
DOI
PubMed
高影响因子
TETRAHEDRON LETTERS
·
2018
·
IF 2.125
Rongxing Zhang,Shengzhou Jin,Yuanxing Wan,Sen Lin,Zhaohua Yan
A novel, efficient, and green protocol to construct C–S bond has been developed via HBr/H 2 O 2 -mediated sulfenylation of styrenes and 4-hydroxycoumarins leading to unsymmetrical sulfides. Various unsymmetrical sulfides were prepared in one step with moderate to good yields using environmentally-friendly H 2 O 2 as oxidant and HBr as catalyst. Based on the preliminary experimental results, a plausible reaction mechanism was proposed for HBr/H 2 O 2 -mediated formation of C–S bond with thiosulfates .
研究领域:
有机化学
·
绿色化学
✓ 已验证
DOI
高影响因子
International Journal of Coal Preparation and Utilization
·
2023
·
IF 2.1
Xuexia Wang,Wencheng Xia,Yaoli Peng,Guangyuan Xie
Iron-assisted pyrolysis (Fe-assisted pyrolysis) is a high-efficiency technique to remove sulfur from low-rank coal. However, the sulfur removal mechanism of Fe-assisted pyrolysis did not compressively address. For filling this gap, this study explored the sulfur removal mechanism of diphenyl sulfone during Fe-assisted pyrolysis based on the factor optimization of desulfurization performance. The iron powder under the optimal conditions of Fe-assisted pyrolysis was characterized with X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS), showing that FeS and some FeS2 were formed on the surface of post-pyrolysis iron powder. Gas chromatography (GC) analysis manifested that the addition of iron powder in the pyrolysis process could considerably reduce the SO2 emission. GC and Fourier transform infrared spectrometer (FTIR) analyses demonstrated that there was C–S bond broken in the diphenyl sulfone structure during Fe-assisted pyrolysis. From the results of thermogravimetry-mass spectrometry (TG-MS), the addition of iron powder in the pyrolysis process could enhance the reaction rate and reduce the temperature required for the reaction. We believe that the results of the present study provided a theoretical basis for a profound understanding of the desulfurization mechanism of Fe-assisted pyrolysis.
研究领域:
能源科学
·
环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2020
·
IF 4.335
Shimin Xie,Lebin Su,Min Mo,Wang Zhou,Yongbo Zhou,Jianyu Dong
An alternative thioesterification reaction via copper-catalyzed oxidative coupling of readily available aroylhydrazides with disulfides is developed, in which oxidative expulsion of N2 overcomes the activation barrier between the carboxylic acid derivatives and the products. The reaction produces various thioesters in good to excellent yields with good functional group tolerance. In the reaction, stable and easily available aroylhydrazides are used as acyl sources and the relatively odorless disulfides are used as S sources. Mechanistic investigations demonstrate that the reaction of copper salt and oxidant (NH4)2S2O8 allows for achievement of tandem processes, including deprotonation, free-radical-mediated denitrogenation, and C–S bond formation.
研究领域:
有机化学
·
催化反应
✓ 已验证
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2020
·
IF 4.335
Nian Zheng,Ce Liu,Ya-Nan Ding,Wei-Yu Shi,Bo-Sheng Zhang,Yong-Min Liang
Copper-catalyzed three-component redox-neutral ring opening of benzothiazoles with aryl iodides and O-benzoyl hydroxylamines for the synthesis of 1-amino-N-(2-(phenylthio)phenyl)methanimine has been developed. This one-pot reaction undergoes C–S and N–O bond cleavage and new C–S and C–N bond construction. Several control experiments excluded a free radical procedure and also demonstrated the secondary amine as a possible intermediate, which was vital to the catalytic reaction. Meanwhile, the deuteration experiment got rid of the C–H activation dehydroisomerization of the benzothiazole mechanism.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Xinpeng Gao,Yuxian Liu,Ying Han,Jing Zhang,Jiwen Guan,Fengping Xiao,Peng Hu,Jiao Gao,Yubao Chen
Room-temperature sodium–sulfur (RT Na-S) batteries are promising candidates for large-scale grid energy storage applications due to the abundant availability of sodium resources and their low acquisition cost. However, the shuttling effect of long-chain sodium polysulfides severely degrades the cycle stability of RT Na-S batteries. In this study, a biomass-derived (corn-straw) porous carbon material with self-doped nitrogen and oxygen atoms was fabricated as a sulfur host (denoted as NOC). Sulfur was subsequently loaded covalently via the vapor-infiltration method to form the cathode material for RT Na-S batteries. Owing to the high cellulose content in corn-straw, the derived NOC composite exhibits excellent electrical conductivity and large pores, which facilitate Na + transport and accommodate the volume expansion of active sulfur during cycling. More importantly, theoretical calculation reveals that compared to pure carbon matrices, the N and O dopants make carbon become unsaturated, increasing the electron density distribution and enhancing bonding ability to form C S bonds. When used as a cathode, in-situ Raman and ex-situ XRD measurements confirm that covalently bonded sulfur inhibits the shuttle effect by directly forming Na 2 S during the reduction reaction. Consequently, the NOC/S cathode delivers superior electrochemical performances with excellent cycle stability. This study introduces an innovative approach to developing advanced RT Na-S batteries by utilizing cost-effective carbon materials derived from biomass.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Fanjing Wei,Xiaoxia Zhang,Junjie Liao,Jiawei Guo,Weiren Bao,Liping Chang
The reactive adsorption desulfurization mechanism of thiophene over Cu/ZnO sorbent in coke oven gas (COG) was established by a combination of theoretical and experimental study. The adsorption behavior of thiophene on Cu surface was studied by density functional theory (DFT) method. The C 4 hydrocarbons releases and sulfur migration over Cu/ZnO sorbent during the thiophene removal process were investigated by comparing with that over CuO, ZnO and CuO+ZnO (prepared by mechanical grinding of CuO and ZnO) sorbents. The results show that the parallel adsorption of thiophene on hexagonal closest packing (HCP) site of Cu (1 1 1) crystal face is the optimal adsorption mode. Cu 0 nanoparticles in Cu/ZnO sorbent have two important roles: (1) adsorb and dissociate H 2 , and (2) cleave the C–S bond of thiophene. The sulfur after the cleavage of C–S bond could transfer directly to ZnO and eventually be converted into ZnS without the intermediate product CuS. During thiophene removal, C 4 H 6 and C 4 H 10 are generated over Cu/ZnO sorbent in the presence of H 2 . ZnO in Cu/ZnO sorbent not only acts as an excellent sulfur accepter, but can greatly affect the adsorption properties by enhancing the spillover and storage of hydrogen atoms . Increasing the interaction between Cu 0 nanoparticles and ZnO to enhance hydrogen spillover is an effective way to improve the thiophene reactive adsorption activity of Cu/ZnO.
研究领域:
化学工程
·
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER RESEARCH
·
2015
·Vol. 22
·期 4
·1-8
·
IF 1.92
Cheng Chuanjie,Bai Xiongxiong,Zhang Xu,Li Hongxia,Huang Qinghua,Tu Yuanming
A symmetric photo-active trithiocarbonate was designed and synthesized, which can act not only as a functional reversible addition-fragmentation chain transfer (RAFT) agent, but also as a crosslinker in crosslinking poly(methyl methacrylate- co -hydroxy ethyl acrylate) (poly(MMA- co -HEA)) due to interactions of benzophenone moieties of trithiocarbonate and hydroxyl groups of poly(MMA- co -HEA) under UV irradiation. In addition, the crosslinked poly(MMA- co -HEA) demonstrates photo-promoted self-healing properties by reshuffling C-S bonds of trithiocarbonate.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Polymer Materials
·
2025
·
IF 4.7
Xiangzhuo Han,Yingchao Zhang,Jinkai Wang,Zhanchen Cui,Zuosen Shi
Sulfonate oxime ester photoinitiators (PIs) based on a thioether-substituted 1,8-naphthalenedicarboximide backbone exhibit good absorption at the emission wavelengths of commonly used LED lamps (385, 395, and 405 nm). The presence of weak C–S and N–O bonds in the molecular structure enables them to be cleaved under light, which leads to the generation of free radicals and cations with efficient initiation properties. Electron paramagnetic resonance spectroscopy supports the mechanism of C–S bond cleavage to produce free radicals, and UV–visible real-time spectroscopy in the presence of Rhodamine B base supports the mechanism of N–O bond cleavage to produce acids. These compounds are high-performance photoinitiators without any other additives for the polymerization of double-bonded compounds and epoxides. They can be initiated at low concentrations when exposed to UV-LEDs. These photoinitiators provide important ideas for the design and synthesis of photoinitiators, which have great potential for application in the field of photopolymerization, especially in hybrid light-curing systems.
研究领域:
材料科学
·
光化学
·
聚合物科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED AND ENVIRONMENTAL MICROBIOLOGY
·
2017
·Vol. 83
·期 23
·
IF 3.807
Cui-Wei Chu,Bin Liu,Na Li,Shi-Gang Yao,Dan Cheng,Jia-Dong Zhao,Ji-Guo Qiu,Xin Yan,Qin He,Jian He
Thiobencarb is a thiocarbamate herbicide used in rice paddies worldwide. Microbial degradation plays a crucial role in the dissipation of thiobencarb in the environment. However, the physiological and genetic mechanisms underlying thiobencarb degradation remain unknown. In this study, a novel thiobencarb degradation pathway was proposed in Acidovorax sp. strain T1. Thiobencarb was oxidized and cleaved at the C—S bond, generating diethylcarbamothioic S-acid and 4-chlorobenzaldehyde (4CDA). 4CDA was then oxidized to 4-chlorobenzoic acid (4CBA) and hydrolytically dechlorinated to 4-hydroxybenzoic acid (4HBA). The identification of catabolic genes suggested further hydroxylation to protocatechuic acid (PCA) and finally degradation through the protocatechuate 4,5-dioxygenase pathway. A novel two-component monooxygenase system identified in the strain, TmoAB, was responsible for the initial catabolic reaction. TmoA shared 28 to 32% identity with the oxygenase components of pyrimidine monooxygenase from Agrobacterium fabrum, alkanesulfonate monooxygenase from Pseudomonas savastanoi, and dibenzothiophene monooxygenase from Rhodococcus sp. TmoB shared 25 to 37% identity with reported flavin reductases and oxidized NADH but not NADPH. TmoAB is a flavin mononucleotide (FMN)-dependent monooxygenase and catalyzed the C—S bond cleavage of thiobencarb. Introduction of tmoAB into cells of the thiobencarb degradation-deficient mutant T1m restored its ability to degrade and utilize thiobencarb. A dehydrogenase gene, tmoC, was located 7,129 bp downstream of tmoAB, and its transcription was clearly induced by thiobencarb. The purified TmoC catalyzed the dehydrogenation of 4CDA to 4CBA using NAD+ as a cofactor. A gene cluster responsible for the complete 4CBA metabolic pathway was also cloned, and its involvement in thiobencarb degradation was preliminarily verified by transcriptional analysis.IMPORTANCE Microbial degradation is the main factor in thiobencarb dissipation in soil. In previous studies, thiobencarb was degraded initially via N-deethylation, sulfoxidation, hydroxylation, and dechlorination. However, enzymes and genes involved in the microbial degradation of thiobencarb have not been studied. This study revealed a new thiobencarb degradation pathway in Acidovorax sp. strain T1 and identified a novel two-component FMN-dependent monooxygenase system, TmoAB. Under TmoAB-mediated catalysis, thiobencarb was cleaved at the C—S bond, producing diethylcarbamothioic S-acid and 4CDA. Furthermore, the downstream degradation pathway of thiobencarb was proposed. Our study provides the physiological, biochemical, and genetic foundation of thiobencarb degradation in this microorganism.
研究领域:
环境微生物学
·
分子生物学
·
生物化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）