Journal of the American Chemical Society
·
2019
·
IF 14.695
Cheng-Jian Zhang,Tian-Cheng Zhu,Xiao-Han Cao,Xin Hong,Xing-Hong Zhang
The synthesis of poly(thioether), a highly desired sulfur-containing polymer, is still a key challenge. Herein, we report a simple and facile approach to poly(thioether)s by closed-system one-pot reaction of carbonyl sulfide (COS) and epoxides. This route underwent the coupling reaction of COS with epoxides, followed by decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing of CO2 and a little bit of COS. Organic base was used as catalyst and initiator in the two steps, respectively. The oxygen/sulfur exchange reaction was driven by successive regioselective elementary reactions and spontaneous releasing of CO2 (COS), leading to the sulfur atom of COS transferring to poly(thioether)s, which was well demonstrated by DFT studies. This work provides an easy-to-handle, metal-free route to poly(thioether)s bearing diverse structures by using readily available chemicals.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 7
·3535-3545
·
IF 3.591
Guanqing Zhang,Xun Kan,Yong Zheng,Yanning Cao,Shijiang Liang,Yihong Xiao,Fujian Liu,Lilong Jiang
A variety of MgAl-layered double hydrotalcites (MA-LDHs-x) with different Mg/Al molar ratios (1 : 3–5 : 1) were prepared by a novel solid-thermal approach. The obtained MA-LDH-x catalysts were characterized by various techniques. These results confirm the successful preparation of MA-LDHs-x with a high degree of crystallinity, large BET surface areas, and unique nanosheet structures with controllable hexagonal morphology. In addition, MA-LDHs-x possess tunable OH− group contents, which could be correlated with the molar ratio of Mg/Al. As a result, the MA-LDH-x catalysts exhibited better catalytic performance in carbonyl sulfide (COS) hydrolysis (COS conversion: 100% at 130 °C for MA-LDHs-3 : 1 vs. 38% at 130 °C for commercial Fe2O3) and H2S selective oxidation (H2S conversion: 100% at 150 °C for MA-LDHs-3 : 1 vs. 41% at 150 °C for commercial Fe2O3) than commercial desulfurization catalysts. Superior activities found in MA-LDH-x catalysts were attributed to their controllable 2D nanosheet structures, and the unique structural characteristics enhance the mass transfer of guest molecules. Notably, the exposed OH− base sites of MA-LDHs-x efficiently activate the acid COS and H2S, which facilitate the COS hydrolysis to H2S, and the selective H2S oxidation to elemental sulfur.
研究领域:
材料科学
·
环境催化
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Bingning Wang,Yeshuang Wang,Zhen Wang,Song Yang,Chao Yang,Jiawei Kou,Huiling Fan,Ju Shangguan
In this study, we report a simple strategy to enhance the low-temperature catalytic performance of γ-Al 2 O 3 for carbonyl sulfide (COS) hydrolysis by regulating the dissociation of H 2 O. Specifically, tetrabutylphosphonium chloride (TBuPC), an ionic liquid, was introduced onto γ-Al 2 O 3 via ultrasonic impregnation. There was a strong interaction between Cl in TBuPC and Al sites in tetrahedral interstices of γ-Al 2 O 3 , and Al sites in octahedral interstices were acted as main adsorption sites of H 2 O. Additionally, the hydrogen bond Cl···H-O lowered the dissociation energy of H 2 O on Al sites in octahedral interstices of γ-Al 2 O 3 , leading to the generation of abundant basic –OH groups, which served as active sites for COS adsorption and hydrolysis. Consequently, 3TBuPC/γ-Al 2 O 3 achieved 100 % COS conversion at 60 °C, which was 2.05 times higher than that of γ-Al 2 O 3 . The catalytic mechanism of COS hydrolysis over 3TBuPC/γ-Al 2 O 3 involved the following steps: (1) H 2 O was adsorbed on the γ-Al 2 O 3 surface and dissociated, generating H* and basic –OH groups; (2) COS was adsorbed on the –OH sites, forming the intermediate HSCO 2 - ; (3) HSCO 2 - reacted with H* to release CO 2 and H 2 S. This significant enhancement provides a new insight for the design and development of low-temperature hydrolysis catalysts.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2019
·
IF 5.997
Cheng-Jian Zhang,Xing-Hong Zhang
Utilization of carbon disulfide (CS2), a low-cost and sulfur-rich one-carbon (C1) feedstock, for making sulfur-containing polymers is important for both polymer chemistry and applied environmental science. However, the production of well-defined sulfur-containing polymers from CS2 and epoxides remains a key challenge. Here, we report a robust coupling reaction of CS2 and epoxides for chemoselectively producing poly(thioether)s and carbonyl sulfide (COS) in one pot. The resultant polymer has exclusive thioether units and a thiol (−SH) terminal. This route takes advantage of oxygen/sulfur exchanges through two consecutive reactions, i.e., cycloaddition of CS2 to epoxides and dethiocarboxylative ring-opening polymerization of the generated cyclic dithiocarbonates. The process can be conducted in ambient air with several commercially available organic bases as catalysts (initiators) and extended to a variety of epoxides, yielding COS and diverse poly(thioether)s with tens of grams. This work furnishes an original and practical strategy for utilizing CS2 as a sulfur feedstock in polymer synthesis.
研究领域:
高分子化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING RESEARCH & DESIGN
·
2023
·
IF 3.9
Xinwei Mu,Liuxing She,Zaikun Wu,Lidan Deng,Jian kong,Tielin Wang,Yuanhang Qin,Yin Zheng
The SBA-15 molecular sieve carrier with large specific surface area and pore volume, high temperature resistance and acid and alkali resistance was successfully synthesized by the method of hydrothermal synthesis . Then, ionic liquid is loaded on the surface and pores of the carrier by the impregnation method, so that it can be combined with the acid-base COS, thereby enhancing the adsorption effect and adsorption selectivity. Effects of three ionic liquids: 1-ethyl-3-methylimidazolium glycinate, 1-butyl-3-methylimidazolium glycinate and 1–(2-Aminoethyl)3-methylimidazolium bromide on the COS adsorption properties were discussed at different adsorption temperatures and loading concentrations. Among these mesoporous molecular sieves immobilized ionic liquids, the result from COS adsorption shows that the specific surface area of SBA-15 molecular sieve impregnated with 0.9 g·mL −1 [C 2 mim][Gly] (SBA-15-C 2 9.0) decreased from 902 m 2 ·g −1 to SBA-15–27 m 2 ·g −1 . And its COS breakthrough adsorption capacity can reach 11.38 mg·g −1 . It can concluded that [C 2 mim][Gly] is helpful to increase the adsorption capacity.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Rui Cao,Xueqian Wang,Ping Ning,Yibing Xie,Langlang Wang,Yixing Ma,Xiang Li,Hui Zhang,Jingye Liu
Basic sites are important to promote carbonyl sulfide (COS) and carbon disulfide (CS 2 ) hydrolysis activity while improving the oxidation resistance of hydrolysis catalysts is a challenge. Here, we report an N -doped alumina-based catalyst ( N -K@Al), where the complete hydrolysis removal of COS and CS 2 by the N -doped catalyst was extended up to 15 h at 160 °C, and the turnover frequency (TOF) value of the catalyst was increased from 0.85 × 10 -2 s −1 to 1.16 × 10 -2 s −1 . The results showed that the strong interaction between nitrogen and potassium decreased the reactive oxygen density and activated –OH, weakening the oxygen mobility. In addition, the beneficial effects of N -doped included the addition of moderately and weakly basic sites by pyridine N. The optimized N -K@Al showed good catalytic performance in the hydrolysis of COS and CS 2 removal with lower reaction temperature and higher total hydrogen sulfide yield. Density functional theory calculations revealed that N -K@Al reduced the Gibbs free energy of COS and CS 2 hydrolysis to 0.21 eV and 0.33 eV, respectively, contributing to the enhanced catalytic activity. The present study presents new strategies for developing efficient antioxidant organosulfur hydrolyzers and other practical industries.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2022
·Vol. 29
·期 56
·84166-84179
·
IF 5.19
Gao Panting,Li Yuran,Lin Yuting,Chang Liping,Zhu Tingyu
Catalytic hydrolysis of carbonyl sulfur (COS) from blast furnace gas is one of the keys to achieving ultra-low emission in the iron–steel industry. To improve the COS hydrolysis activity on γ-Al 2 O 3 catalyst at low temperature, catalysts with Fe or La as the active component were prepared by the impregnation method, the physical and chemical properties of the catalyst were characterized by ICP, XRF, XRD, BET, and TPD. The hydrolysis activity of COS and sulfur resistance ability on various catalysts were investigated in a fixed bed reactor combined with gas chromatography. The results show that the addition of Fe or La improves the COS hydrolysis activity due to the increase in alkaline sites on the catalyst surface. The roles of various alkaline sites on catalysts have been recognized. The weak alkaline center is the reaction site of COS hydrolysis, the middle and strong alkaline centers are the adsorption and oxidation sites of H 2 S. The Fe/Al 2 O 3 catalyst has higher hydrolytic activity and oxidative capacity for H 2 S removal due to forming more sulfate species on Fe. The La/Al 2 O 3 catalyst has higher hydrolysis efficiency in that H 2 S rapidly desorbs from the catalyst surface to the gas phase, and then, the activity of reaction sites is recovered. This provides an idea for the preparation of sulfur-resistant catalysts.
研究领域:
环境科学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
·
2018
·Vol. 2018
·期 48
·6983-6990
·
IF 2.882
Bohao Zhou,Hailong Hong,Hongcai Wang,Tianmiao Zhang,Limin Han,Ning Zhu
Graphical An efficient method for preparing benzothiazolone derivatives was developed by a domino coupling reaction between the disulfide and COS in the present of NaOH. Notably, the C=O of COS was converted into benzothiazolone by carbonylation reaction and the sulfur of COS was transformed into sulfur and sulfide after cleaving the S–S bond under mild conditions. This efficient synthetic methodology could provide a promising process for the utilization of COS. Carbonyl sulfide (COS), whose molecular structure is similar to CO 2 and CS 2 , could be used as a better alternative carbonyl reagent due to its high chemical activity. However, the unfriendly by-product H 2 S would be generated when COS is used as a carbonyl reagent in the carbonylation reaction. In this report, the odorless and stable disulfide was used to replace the traditional foul smelling and unstable o -aminobenzenethiol to react with COS for preparing benzothiazolone derivatives in excellent yield, in which coupling reaction of H 2 S generation and S–S bond cleavage was firstly designed. Notably, the C=O of COS was converted into benzothiazolone derivatives by carbonylation reaction and the sulfur of COS was transformed into sulfur and sulfide after cleaving the S–S bond by a domino reaction of disulfide and COS under mild conditions. This efficient synthetic methodology provided a promising process for the utilization of COS.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Kaixuan Yan,Xin Song,Chunliang Zhou,Junnan Liu,Rongji Cui,Panting Gao,Zhicheng Tang
The presence of sulfur-containing impurities in natural gas not only diminishes its utilization value, but also results in the emission of sulfur-containing pollutants. In this study, a Cu-Ce bimetallic-loaded MCM-41 catalyst was prepared by ammonia evaporation method for the catalytic hydrolysis of carbonyl sulfide (COS). The desulfurization efficiency of Cu 25 Ce 5 /MCM-41 can reach a 100 % COS removal rate and maintain for 3.5 h. CuO furnishes the predominant weakly acidic and weakly basic sites for the desulfurization process, which are conducive to the adsorption of COS. Meanwhile, CeOx provides a greater abundance of moderately basic sites for the desulfurization process, which help to improve the removal efficiency of COS. The incorporation of Ce into the catalyst enhances the resistance to sulfur poisoning of Cu and prolongs the lifespan of the catalyst. The incorporation of Ce is capable of transforming the strongly basic sites on the surface of Cu 25 /MCM-41 into moderately basic sites, avoiding excessive oxidation of H 2 S. Additionally, the introduction of Ce offers a degree of protection for CuO, which improves the ability of the catalyst to resist sulfur poisoning. The combined effect of Cu and Ce was found to be instrumental in enhancing the adsorption of COS and in slowing down the oxidation of H 2 S. The reduction of Cu 2+ and Ce 3+ indicated their direct participation in the oxidation of H 2 S. Firstly, COS adsorbed on the catalyst surface is converted into H 2 S and CO 2 through a catalytic hydrolysis reaction. Subsequently, H 2 S adsorbed on the catalyst surface undergoes partial oxidation to sulfide, and partial further oxidation by oxygen-containing functional groups on the surface to S, SO 3 2- , and SO 4 2- , which results in the toxic deactivation of the catalyst.
研究领域:
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Chemistry-An Asian Journal
·
2024
·Vol. 19
·期 21
·e202400235
·
IF 3.5
Shuangyan Zi,Kai Li,Xueqi Wang,Lina Sun,Yu Tian,Bei Huang,Heping Zeng,Yixing Ma
This study utilized a hydrothermal method to synthesize various metal-modified rod-like ceria catalysts (Fe, Co, Cu, Ni, La), achieving efficient COS removal at low temperatures. The research identified surface oxygen vacancies and basic sites as critical factors that influence the catalytic performance of COS hydrolysis. The addition of different metals to pristine ceria rods increased the specific surface area, oxygen vacancy content (Ov), and basicity, which enhanced the catalysts′ sulfur resistance and stability. Among all the catalysts tested, 10La-CeO 2 demonstrated the highest COS removal rate. This is because La doping significantly augmented Ov, providing more H 2 O adsorption and activation sites. Furthermore, 10La-CeO 2 showed enhanced Lewis basicity, making it easier for COS to adsorb and promote hydrolysis. The in situ DRIFTS results confirmed that appropriate oxygen vacancies and basic sites favored the formation of intermediates such as HCO 3 − and HSCO 2 − , promoting the decomposition of COS into H 2 S and CO 2 .
研究领域:
催化化学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Nan Shi,Hengxi Zhu,Jiamin Qi,Bin Li,Jin Zhang
Carbonyl sulfur (COS) was difficult to be removed by conventional desulfurization technologies because of its stable chemical properties. Mesoporous γ-Al 2 O 3 (MA) showed excellent potential for hydrolysis of COS, but the catalyst life was greatly shortened with the progress of the reaction. Therefore, improving the catalyst life is the key to MA which can apply to hydrolysis of COS. In this study, P123 modified mesoporous γ-Al 2 O 3 (P-MA) catalyst was prepared by sol–gel method, and it was regulated by template agent and acidity regulator. These preparation conditions of P-MA were optimized to improve the hydrolysis efficiency of COS. The effects of temperature, space velocity, relative humidity and oxygen concentration for the hydrolysis efficiency of COS were studied. The results show that the optimized P-MA catalyst is suitable for COS low-temperature hydrolysis reaction, and it can maintain 99 % for 10 h under the tough reaction conditions. The only crystal of P-MA was γ-Al 2 O 3 with large specific surface area and uniform distribution pore, which are beneficial to the COS hydrolysis. In addition, the hydrolysis efficiency of COS can also remain 97 % for 10 h in the O 2 and CO 2 atmosphere, indicating that the P-MA catalyst has a specific anti-poisoning ability. The kinetics and reaction mechanism of COS catalytic hydrolysis were studied, which showed that the adsorption of H 2 S was the key to hindering the continuous reaction. The P-MA can effectively inhibit the adsorption of H 2 S, which greatly improved COS hydrolysis life of P-MA. This study provided a theoretical basis for the application of Al 2 O 3 catalyst in the COS hydrolysis.
研究领域:
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2025
·
IF 2.7
Munir Ullah Khan,Muhammad Naeem Shah,Safir Ullah Khan,Chengjian Zhang,Xinghong Zhang
This study investigates the development of the iron-based catalyst FeFe-DMCC for the efficient copolymerization of carbonyl sulfide (COS) and propylene oxide (PO), leading to the production of poly(propylene monothiocarbonate)s (PPMTC). The resulting polymers exhibit number-average molecular weights ( M n ) ranging from 36.6 to 91.8 kg mol −1 , with polydispersity indices ( Đ ) between 1.7 and 4.8. The FeFe-DMCC catalyst demonstrated exceptional performance, achieving polymer yields of up to 1058 grams per gram of catalyst within a 12-h reaction period. A significant breakthrough in this work is the catalyst's ability to effectively suppress the oxygen-sulfur exchange reaction (O/S ER), a side reaction that typically generates mixed linkages. Instead, the process achieved outstanding selectivity, exceeding 99%, for monothiocarbonate units, with no formation of cyclic thiocarbonate byproducts. This remarkable control underscores the catalyst's efficiency in producing clean, well-defined polymers. Additionally, the copolymer composition, particularly the ratio of monothiocarbonate to ether units, can be finely tuned by varying the COS feed ratio, enabling precise customization of the polymer's properties. These findings establish FeFe-DMCC as a highly effective and selective catalyst for COS/PO copolymerization, offering a pathway to produce high-quality PPMTC with tailored characteristics and minimal byproduct formation. This work represents a significant advancement in sustainable materials development.
研究领域:
材料科学
·
催化化学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）