Reaction Chemistry & Engineering最新文献

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Microcrystalline cellulose-based, nitrogen-doped carbon nanoflakes for adsorption of uranium and thorium† 微晶纤维素基,氮掺杂碳纳米片对铀和钍†的吸附
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-05-06 DOI: 10.1039/D4RE00613E
Kiran Gupta, Ruchi Aggarwal, Manish Sharma, Ranju Yadav, Ragini Gupta, Gunnar Westman and Sumit Kumar Sonkar
{"title":"Microcrystalline cellulose-based, nitrogen-doped carbon nanoflakes for adsorption of uranium and thorium†","authors":"Kiran Gupta, Ruchi Aggarwal, Manish Sharma, Ranju Yadav, Ragini Gupta, Gunnar Westman and Sumit Kumar Sonkar","doi":"10.1039/D4RE00613E","DOIUrl":"https://doi.org/10.1039/D4RE00613E","url":null,"abstract":"<p >Nitrogen-doped carbon nanoflakes (N-CNFs) were synthesized <em>via</em> a simple acid-assisted carbonization process using microcrystalline cellulose (MCC) and urea. The as-synthesized N-CNFs were used for the adsorption of simulated radioactive nuclides such as uranium [U(<small>VI</small>)] and thorium [Th(<small>IV</small>)]. Under optimized experimental conditions, N-CNFs removed ≈45.6 and ≈48.7 ppm of U(<small>VI</small>) and Th(<small>IV</small>), respectively. U(<small>VI</small>) and Th(<small>IV</small>) adsorption followed the Langmuir and pseudo-second-order kinetic models. The effect of pH, concentration, and loading capacity was also explored. Furthermore, adsorption–desorption studies were conducted to evaluate the recyclability of N-CNFs as an adsorbent, which demonstrated good recyclability efficiency for four cycles.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1767-1775"},"PeriodicalIF":3.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advanced adsorptive removal of dimethyl phthalate from water using a tertiary amine-functionalized polymeric resin: insights into experimental design and statistical analysis 使用叔胺功能化聚合树脂从水中吸附去除邻苯二甲酸二甲酯:对实验设计和统计分析的见解
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-05-05 DOI: 10.1039/D5RE00124B
Kübranur Türekkan, Yaşar Kemal Recepoğlu, Duygu Ova Özcan and Özgür Arar
{"title":"Advanced adsorptive removal of dimethyl phthalate from water using a tertiary amine-functionalized polymeric resin: insights into experimental design and statistical analysis","authors":"Kübranur Türekkan, Yaşar Kemal Recepoğlu, Duygu Ova Özcan and Özgür Arar","doi":"10.1039/D5RE00124B","DOIUrl":"https://doi.org/10.1039/D5RE00124B","url":null,"abstract":"<p >This study investigates the effective removal of dimethyl phthalate (DMP) from aqueous solutions using Purolite Macronet MN100, a polymer-based adsorbent containing tertiary amine functional groups. A series of batch experiments was performed to assess the influence of resin dosage and solution pH, while adsorption kinetics were analyzed to determine the optimal contact time and the underlying rate-limiting mechanism. Equilibrium data were interpreted using adsorption isotherm models, and thermodynamic parameters (Δ<em>G</em>°, Δ<em>H</em>°, and Δ<em>S</em>°) were calculated to evaluate the feasibility and spontaneity of the process. Additionally, the effect of common coexisting ions in wastewater (Na<small><sup>+</sup></small>, K<small><sup>+</sup></small>, Mn<small><sup>2+</sup></small>, Ca<small><sup>2+</sup></small>, Mg<small><sup>2+</sup></small>) on DMP removal was examined. The optimum removal efficiency (&gt;97%) was achieved using 0.02 g of resin per 25 mL solution at pH 2–6, with equilibrium established within 300 minutes. The adsorption behavior was best described by the Langmuir isotherm, indicating monolayer adsorption with a maximum capacity of 463.37 mg g<small><sup>−1</sup></small>. Mechanistic evaluation revealed that π–π interactions and hydrogen bonding were the dominant forces driving DMP adsorption. The presence of competing cations had minimal impact, demonstrating the adsorbent's strong selectivity toward DMP. Desorption studies showed complete DMP recovery using absolute ethanol (&gt;99%), with &gt;99% regeneration efficiency. Optimization using Central Composite Design (CCD) under Response Surface Methodology (RSM) produced a statistically robust model (<em>R</em><small><sup>2</sup></small> = 0.98), consistent with the experimental results. Overall, Purolite MN100 proved to be a highly efficient, selective, and regenerable adsorbent suitable for DMP removal in wastewater treatment processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1897-1909"},"PeriodicalIF":3.4,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680965","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
New-fashioned MnOx/g-C3N4@ZIF-8 catalyst for the liquid-phase selective oxidation of toluene in the absence of solvent or additives† 新型MnOx/g-C3N4@ZIF-8催化剂在无溶剂或添加剂的情况下液相选择性氧化甲苯†
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-05-01 DOI: 10.1039/D5RE00058K
Sihang Lu, Wenkai Chen, Gui Chen, Shaobin Deng, Dexuan Xiang, Haizhou Zhang, Yuanxiang Li, Bailin Xiang and Ye Yuan
{"title":"New-fashioned MnOx/g-C3N4@ZIF-8 catalyst for the liquid-phase selective oxidation of toluene in the absence of solvent or additives†","authors":"Sihang Lu, Wenkai Chen, Gui Chen, Shaobin Deng, Dexuan Xiang, Haizhou Zhang, Yuanxiang Li, Bailin Xiang and Ye Yuan","doi":"10.1039/D5RE00058K","DOIUrl":"https://doi.org/10.1039/D5RE00058K","url":null,"abstract":"<p >A new-fashioned MnO<small><sub><em>x</em></sub></small>/g-C<small><sub>3</sub></small>N<small><sub>4</sub></small>@ZIF-8 catalyst was synthesized by a co-precipitation method. It exhibited good catalytic performance in the liquid-phase selective oxidation of toluene in the absence of solvent or additives. Series characterization confirmed the doping of Mn in the catalyst and large specific surface area, which resulted in high catalytic activity and high target product selectivity. The optimal reaction was conducted at 180 °C for 2.0 h, with 0.1 g of catalyst and oxygen pressure of 1.0 MPa. The toluene conversion was 4.7%, the selectivity to benzaldehyde and benzyl alcohol (BAL + BOL), and benzoic acid (BAC) was 74.3%, and 18.2%, respectively. In addition, a possible oxidation reaction pathway was postulated. The catalyst has low cost and high selectivity to BAL + BOL, which is of great industrial importance for the highly selective production of BAL and BOL from toluene.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1758-1766"},"PeriodicalIF":3.4,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Physicochemical aspects of solid phase synthesis using cross-linked polymeric matrices 使用交联聚合物基质的固相合成的物理化学方面
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-29 DOI: 10.1039/D5RE00115C
Sebastián Pinzón-López, Eric T. Sletten, Matthias Kraume, Peter H. Seeberger and José Danglad-Flores
{"title":"Physicochemical aspects of solid phase synthesis using cross-linked polymeric matrices","authors":"Sebastián Pinzón-López, Eric T. Sletten, Matthias Kraume, Peter H. Seeberger and José Danglad-Flores","doi":"10.1039/D5RE00115C","DOIUrl":"https://doi.org/10.1039/D5RE00115C","url":null,"abstract":"<p >Solid phase synthesis (SPS) offers a bottom-up approach for assembling (bio-)oligomers and polymers with precise molecular detail. Although SPS has been applied to various organic compounds, it is expressly convenient for assembling biopolymers. Fundamental studies and optimization efforts have focused solely on organic chemistry aspects, often neglecting physicochemical issues. Here, we summarize the current understanding of the physical phenomena occurring in the gel-like, solvent-swollen polymer beads used commonly as a solid support, aiming to help advance SPS by providing new insights based on physicochemical principles.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1442-1454"},"PeriodicalIF":3.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re00115c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Lead titanate-modified perovskite with silver and cobalt as a superior photocatalyst toward the conversion of methylene blue 钛酸铅修饰钙钛矿与银和钴作为亚甲基蓝转化的优良光催化剂
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-29 DOI: 10.1039/D4RE00546E
Amin Yousefvand, Mahdieh Ghobadifard and Sajjad Mohebbi
{"title":"Lead titanate-modified perovskite with silver and cobalt as a superior photocatalyst toward the conversion of methylene blue","authors":"Amin Yousefvand, Mahdieh Ghobadifard and Sajjad Mohebbi","doi":"10.1039/D4RE00546E","DOIUrl":"https://doi.org/10.1039/D4RE00546E","url":null,"abstract":"<p >Lead titanate perovskite (PbTiO<small><sub>3</sub></small>) and Ag–Co co-doped PbTiO<small><sub>3</sub></small> (Ag–Co-PTO) nanoparticles were obtained by a hydrothermal procedure. The prepared samples were characterized by physicochemical techniques, and the phase, morphology, elemental composition, and optical properties were analyzed. To investigate the impact of the as-prepared photocatalyst on dye conversion, several parameters, like pH conditions in the presence of the different amounts of catalyst and oxidant at various temperatures, were optimized. At pH = 5, the Ag–Co-PTO photocatalyst converted 88% of methylene blue (MB) within 40 min under a visible lamp. The superior photo-performance of Ag–Co-PTO is due to the powerful electronic interaction among Ag, Co, and perovskite, which promotes the transfer and separation of charges. Besides, the predicted photocatalytic mechanism of Ag–Co-PTO and its stability tests are considered. Typically, Ag–Co-PTO highlights a promising opportunity for the conversion of pollutants.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1665-1675"},"PeriodicalIF":3.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Stepwise pretreatment involving dilute acid and amine for corn stover fractionation toward full lignocellulose-oriented valorization† 逐步预处理涉及稀酸和胺的玉米秸秆分馏,以充分木质纤维素为导向的增值†
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-28 DOI: 10.1039/D5RE00122F
Samuel Ntakirutimana, Jian-Wei Zhang, Tao Xu, He Liu, Jia-Qi Cui, Tao Shi, Zhi-Hua Liu, Bing-Zhi Li and Ying-Jin Yuan
{"title":"Stepwise pretreatment involving dilute acid and amine for corn stover fractionation toward full lignocellulose-oriented valorization†","authors":"Samuel Ntakirutimana, Jian-Wei Zhang, Tao Xu, He Liu, Jia-Qi Cui, Tao Shi, Zhi-Hua Liu, Bing-Zhi Li and Ying-Jin Yuan","doi":"10.1039/D5RE00122F","DOIUrl":"https://doi.org/10.1039/D5RE00122F","url":null,"abstract":"<p >Lignocellulose valorization is interwoven with fractionation and by tuning the pretreatment setup and conditions, the characteristics of both polysaccharides and lignin could be tailored to match upgrading demands. Here, a stepwise pretreatment approach involving dilute acid and amine was developed for corn stover fractionation. Under the optimized prehydrolysis conditions (3% H<small><sub>2</sub></small>SO<small><sub>4</sub></small>, 120 °C and 2 h), up to ∼97.8% of original xylan was released in the form of xylose, along with a negligible amount of furfural. The signal patterns of confocal laser scanning microscopy revealed that the removal of hemicellulose caused lignin redistribution within the cell wall. At high biomass loading (58%, w/w), amine pretreatment extracted up to ∼82% of lignin with abundant β-O-4 linkages (37–41/100Ar) and strong fluorescence (turquoise and light blue). Enzymatic hydrolysis of mechanochemically pretreated cellulose (MCC) and thermochemically pretreated cellulose (TCC) resulted in glucan conversion of 96.1 and 92.8%, respectively, at 30 mg Cellic® CTec3 HS/g for 72 h. Furthermore, mass balance demonstrated that the combined dilute acid–amine pretreatment could potentially be an efficient fractionation method for lignocellulose. Moreover, a mechanistic understanding of the interactions between lignocellulose components and pretreatment solvents is described. Overall, this pretreatment approach offers the right balance between fractionation of all lignocellulose constituents and preservation of their structural integrity, while simultaneously opening a window for lignin functionalization and depolymerization.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1828-1844"},"PeriodicalIF":3.4,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Expression of Concern: Immobilized tetrakis(triphenylphosphine)palladium(0) for Suzuki–Miyaura coupling reactions under flow conditions 关注表达:流动条件下固定化四(三苯基膦)钯(0)用于Suzuki-Miyaura偶联反应
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-24 DOI: 10.1039/D5RE90015H
G. Valerie Ramaotsoa, Ian Strydom, Jenny-Lee Panayides and Darren Riley
{"title":"Expression of Concern: Immobilized tetrakis(triphenylphosphine)palladium(0) for Suzuki–Miyaura coupling reactions under flow conditions","authors":"G. Valerie Ramaotsoa, Ian Strydom, Jenny-Lee Panayides and Darren Riley","doi":"10.1039/D5RE90015H","DOIUrl":"https://doi.org/10.1039/D5RE90015H","url":null,"abstract":"<p >Expression of Concern for ‘Immobilized tetrakis(triphenylphosphine)palladium(0) for Suzuki–Miyaura coupling reactions under flow conditions’ by G. Valerie Ramaotsoa <em>et al.</em>, <em>React. Chem. Eng.</em>, 2019, <strong>4</strong>, 372–382, https://doi.org/10.1039/C8RE00235E.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1429-1429"},"PeriodicalIF":3.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re90015h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The kinetics of aqueous lactose hydrolysis with sulfuric acid† 硫酸水解乳糖的动力学研究
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-23 DOI: 10.1039/D5RE00175G
Wenjia Wang, Owen J. Dziedzic, Claire R. Lesnjak, Zhuoqian Yu, James Miller, Xiaolei Shi, Jarryd R. Featherman, Scott A. Rankin and George W. Huber
{"title":"The kinetics of aqueous lactose hydrolysis with sulfuric acid†","authors":"Wenjia Wang, Owen J. Dziedzic, Claire R. Lesnjak, Zhuoqian Yu, James Miller, Xiaolei Shi, Jarryd R. Featherman, Scott A. Rankin and George W. Huber","doi":"10.1039/D5RE00175G","DOIUrl":"https://doi.org/10.1039/D5RE00175G","url":null,"abstract":"<p >Lactose-rich Greek yogurt acid whey (GAW) is a waste stream in the dairy industry that has caused severe environmental and economic challenges to the U.S. agricultural communities. Lactose is a sugar found in dairy products that has a low sweetness value and is often difficult to digest. Lactose can be hydrolyzed into glucose–galactose syrups (GGS). However, 5-hydroxymethylfurfural (HMF) is formed which must be removed for the GGS to be used as an alternative sustainable sweetener. In this study, we model lactose hydrolysis and include the first detailed kinetic investigation of HMF formation during sulfuric-acid-catalyzed lactose hydrolysis. We systematically examined the effects of temperature, lactose concentration, pH, and reaction time on the hydrolysis process, proposed 57 possible reaction networks, and developed a kinetic model accurately describing lactose hydrolysis and HMF formation, and calculated key kinetic parameters. Our model demonstrated strong alignment with experimental data and allowed us to simulate optimal conditions for maximizing GGS yield over 89% while minimizing HMF formation by 75–80%. This study provides valuable insights for optimizing reactor design and operational strategies, improving the economic viability and sustainability of GAW valorization.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1676-1691"},"PeriodicalIF":3.4,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Ag-doped Ni/SiO2 catalysts for the synthesis of aromatic amines from aromatic phenol† 用掺银Ni/SiO2催化剂从芳香酚†合成芳香胺
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-22 DOI: 10.1039/D5RE00055F
Kun Li, Baicheng Feng, Meng Guo, Rong Qu and Yan Jin
{"title":"Ag-doped Ni/SiO2 catalysts for the synthesis of aromatic amines from aromatic phenol†","authors":"Kun Li, Baicheng Feng, Meng Guo, Rong Qu and Yan Jin","doi":"10.1039/D5RE00055F","DOIUrl":"https://doi.org/10.1039/D5RE00055F","url":null,"abstract":"<p >Aromatic primary amines are chemical products and raw materials with a wide range of applications. However, synthesis of primary aromatic amines relies heavily on non-renewable petrochemicals as feedstock. We have prepared a catalyst for Ni/SiO<small><sub>2</sub></small> doped Ag, and a process has been instituted to prepare aromatic primary amines, which use renewable resources as raw materials through a fixed bed reactor under ambient pressure conditions. The catalyst and process were validated using phenol synthesis of aniline as a template reaction. The resultant surface phenol conversion is 99% and aniline selectivity is 98.5%, and the by-product of the reaction is water, which is in line with the principles of green chemistry. The broad applicability of the catalysts and synthesis process was further verified by the synthesis of aromatic primary amines using the corresponding aromatic phenols. The catalysts were characterized using TEM, SEM, BET, XPS and XRD techniques to fully analyze their morphology, microstructure and elemental composition. The adsorption model was constructed based on the characterization results, and the density functional theory (DFT) calculations confirmed that after doping Ag, phenol formed shorter chemical bonds at the active site of Ni–Ag bimetal through chemical adsorption, which indicated that it had stronger adsorption energy for phenol, and the amount of electron transfer from the active site of Ni–Ag bimetal to phenol was 2.9 fold higher than that before doping, which significantly promoted the activation of reactants.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1596-1605"},"PeriodicalIF":3.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Aminopropylimidazole and its zinc complex: CO2 chemistry and catalytic synthesis of cyclic carbonates† 氨基丙基咪唑及其锌配合物:CO2化学和催化合成环状碳酸盐†
IF 3.4 3区 化学
Reaction Chemistry & Engineering Pub Date : 2025-04-22 DOI: 10.1039/D5RE00073D
Feda'a M. Al-Qaisi, Abdussalam K. Qaroush, Ahmad M. Ala'mar, Ala'a F. Eftaiha, Khaleel I. Assaf and Timo Repo
{"title":"Aminopropylimidazole and its zinc complex: CO2 chemistry and catalytic synthesis of cyclic carbonates†","authors":"Feda'a M. Al-Qaisi, Abdussalam K. Qaroush, Ahmad M. Ala'mar, Ala'a F. Eftaiha, Khaleel I. Assaf and Timo Repo","doi":"10.1039/D5RE00073D","DOIUrl":"https://doi.org/10.1039/D5RE00073D","url":null,"abstract":"<p >The biomimicry of carbonic anhydrase as the interaction between zinc and imidazole serves as an inspiration to engineer synthetic systems for CO<small><sub>2</sub></small> capture and utilization. In this research, we developed a zinc–aminopropylimidazole (Zn–api) complex to achieve CO<small><sub>2</sub></small> insertion and subsequently catalyze its cycloaddition reaction with a variety of epoxides. We investigated the complexation and carbamation reactions of both the unbound ligand and its zinc complex in aqueous and DMSO solutions. In D<small><sub>2</sub></small>O, unbound api reacts with CO<small><sub>2</sub></small> through a 1 : 2 mechanism, forming ammonium carbamate. However, in DMSO-<em>d</em><small><sub>6</sub></small>, the reaction follows a 1 : 1 pathway and leads to carbamic acid. Interestingly, the Zn–api complex captures CO<small><sub>2</sub></small> differently depending on the solvent, forming an uncharged species (–NHCO<small><sub>2</sub></small>–Zn) in water and a zwitterionic carbamate (–NH<small><sub>2</sub></small><small><sup>+</sup></small>Br<small><sup>−</sup></small>–CO<small><sub>2</sub></small>–Zn–Im) in DMSO. To our knowledge, a first time zwitterionic carbamate coordination mode <em>via</em> CO<small><sub>2</sub></small> insertion is verified by <em>in situ</em> ATR-FTIR with a peak centered at 1704 cm<small><sup>−1</sup></small> and further supported by quantum chemical calculations. The latter complex exhibits excellent catalytic performance for cyclic carbonates synthesis, achieving 94% and 96% conversion for epichlorohydrin carbonate and glycidol carbonate, respectively, under ambient reaction conditions using a CO<small><sub>2</sub></small> balloon. Notably, it demonstrates remarkable stability over five consecutive catalytic cycles for the coupling of epichlorohydrin and CO<small><sub>2</sub></small> without a discernible decrease in activity.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1461-1472"},"PeriodicalIF":3.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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