Reaction Chemistry & Engineering最新文献

{"title":"Gas–liquid flow synthesis of Zn3N2-quantum dots†","authors":"Malin G. Lüdicke, Jonas Schramm, Martin Wichert and Ralph A. Sperling","doi":"10.1039/D4RE00548A","DOIUrl":"https://doi.org/10.1039/D4RE00548A","url":null,"abstract":"<p >Continuous process engineering leads production of fine chemicals to a new level of industrialisation. This study elaborates specifications, benefits and pitfalls for the biphasic, high-temperature synthesis of Zn<small>₃</small>N<small>₂</small> quantum dots, which are made from inexpensive and earth-abundant starting materials. A micro-flow tubular reactor equipped with inline/online process sensors and a product analysis device is used. All technical requirements are fulfilled for the corrosive gas and air-sensitive starting and product materials to create a safe pilot plant for reproducible nanoparticle synthesis. The process parameter window yields tunable fluorescent nanocrystals (506–710 nm, 4–10 nm) which broadly match in quality (FWHM: 99–186 nm, QY: 15–56%) with those made in a batch approach. The transfer to a continuous synthesis practice greatly improves throughput because time is reduced as the reaction scheme can be realised in a single process step. In addition, handling effort is minimised with inline reagent dilution and optical spectroscopy which allows product adaptation by tuning of the process parameters in real-time.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1291-1301"},"PeriodicalIF":3.4,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00548a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148242","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}

{"title":"Bridging molecular dynamics and process engineering to predict the chemical recyclability of polyurethane foams†","authors":"Christophe de Graaf, Jonas Cassimon, Attila Kovacs, Matthew Porters, Christophe M. L. Vande Velde, Philippe Nimmegeers, Ana V. Cunha and Pieter Billen","doi":"10.1039/D4RE00505H","DOIUrl":"https://doi.org/10.1039/D4RE00505H","url":null,"abstract":"<p >Polyurethanes are versatile materials, but their thermoset nature limits mechanical recycling as they do not melt under heating. However, chemical recycling by depolymerization does not yet provide complete circularity, given the highly diverse monomers and additives. Especially for rigid foams, with short and multifunctional polyols, the separation of depolymerization products is challenging. In this paper, we propose a strategy to screen the separation of these products <em>via</em> liquid–liquid extraction by comparing molecular dynamics simulations with experimental results performed on a synthesized model rigid foam depolymerised by hydrolysis. Bifunctional ethyleneoxide polyols with molecular weights of 200, 400, 600 and 1000 are used together with 4,4′-methylene dianiline (MDA). The tested solvent systems are acetonitrile/<em>n</em>-hexane, water/dichloroethane, water/ethyl acetate and water/<em>n</em>-octanol. Coarse-grained (CG) molecular dynamics simulations were used to model the large-scale morphological organization during solution-processing. Our results show a clear separation between the polyols and the depolymerised aromatic components, except for the acetonitrile/<em>n</em>-hexane solvent system, where all solutes dissolve in acetonitrile. Polyols preferentially migrate to the aqueous phase, while aromatic amines such as MDA favour the organic phase. The simulations reveal that larger polyols tend to accumulate at the interface, particularly in the water/dichloroethane and water/ethyl acetate systems. Experimental partition coefficients, consistent with simulation predictions within error margins reported for the Martini 3 forcefield, indicate a strong correlation between polyol molecular weight and phase behaviour. This separation is further influenced by solvent polarity, with water/<em>n</em>-octanol systems exhibiting 2–3 times more MDA aggregation than the other systems, as predicted by the analysis of radial distribution functions and density profiles. The combined approach of molecular dynamics and experimental validation offers a promising strategy for optimizing liquid–liquid extraction in polyurethane depolymerization, guiding future design-for-circularity processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1268-1279"},"PeriodicalIF":3.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148240","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}

{"title":"Synergistic effect of graphitic carbon nitride in enhancing flame-retardant properties of polypropylene composites","authors":"Vinod Sharma, Shilpi Agarwal, Shailey Singhal, Shikha Wadhwa and Ashish Mathur","doi":"10.1039/D4RE00590B","DOIUrl":"https://doi.org/10.1039/D4RE00590B","url":null,"abstract":"<p >Conventional flame retardants based on polymeric materials demonstrate high flammability, producing huge amounts of smoke, toxic gases and melt drips upon burning, causing immense damage to living beings and the environment. The use of brominated organic compounds, although effective, is discouraged due to their adverse effects and ubiquitous nature. In the present study, an intumescent flame-retardant (IFR) system (g-CN@3P) is developed by compounding different amounts of g-CN as a synergist with piperazine pyrophosphate (3P) in polypropylene (PP). SEM and XPS clearly demonstrate the interaction between g-CN and 3P, leading to enhanced flame-retardant properties of 3P. An IFR containing just 1.5 g of g-CN passed the vertical burning test (UL-94) with V0 rating. High flame retardancy of the composite makes it suitable for use in applications where high flame resistance is crucial. The composition also achieved an increase in limiting oxygen index (LOI) of 21.3% compared to the composition without the g-CN synergist. Moreover, the peak heat release rate, total heat release and smoke optical density were also reduced appreciably by 62.6%, 42.6% and 17.6%, respectively. The optimum composition of PP/g-CN@3P improved the mechanical properties compared to PP/3P samples. This study emphasizes the potential of graphitic carbon nitride additives as an environmentally friendly alternative to brominated organic compounds, offering a sustainable approach to enhancing flame-retardant properties.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1280-1290"},"PeriodicalIF":3.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148241","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}

{"title":"Continuous flow synthesis of functionalized biaryl compounds via a benzyne intermediate†","authors":"Chaoming Liang, Weixia Lin, Zilong Lin, Runxiang Yu, Yuyan Kang, Xiangmin Sang, Maolin Sun, Yueyue Ma, Ruihua Cheng and Jinxing Ye","doi":"10.1039/D5RE00023H","DOIUrl":"https://doi.org/10.1039/D5RE00023H","url":null,"abstract":"<p >A continuous flow protocol for the preparation of benzyne was developed utilizing readily accessible 1-bromo-2-iodobenzene and <em>i</em>PrMgCl·LiCl. The halogen–magnesium exchange and subsequent elimination reactions were conducted at temperatures of 0 °C and 80 °C, respectively, resulting in the generation of a highly reactive benzyne intermediate within minutes. The <em>in situ</em> generated benzyne can be efficiently employed in the continuous flow synthesis of functionalized biaryl compounds, including a series of ligands commonly utilized in Buchwald–Hartwig cross-coupling reactions.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1359-1364"},"PeriodicalIF":3.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148229","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}

{"title":"Hydride-mediated chemoselective C–H bond formation during benzoic acid hydrodeoxygenation on anatase TiO2†","authors":"Mikyung Hwang, Jeremy Hu, Michael J. Janik and Konstantinos Alexopoulos","doi":"10.1039/D4RE00561A","DOIUrl":"https://doi.org/10.1039/D4RE00561A","url":null,"abstract":"<p >The chemoselective hydrogenation of benzoic acid to aromatic products such as benzaldehyde, benzyl alcohol, toluene, and benzene is studied on anatase TiO<small>₂</small> (001) using density functional theory (DFT) and microkinetic modeling (MKM). Oxygen vacancy (O<small>_vac</small>) sites are more active for benzoic acid hydrogenation than fully oxidized surface regions, with a nearly 2.5 eV lower energy for the first C–H bond formation reaction to occur near O<small>_vac</small>. This favorable C–H bond formation mechanism on anatase TiO<small>₂</small> occurs between hydrides (H<small>⁻</small>) and monoanionic intermediates coadsorbed in O<small>_vac</small>. A steady-state microkinetic model is constructed using computed reaction energies and activation barriers to determine rates of product formation at different reaction temperatures. Product selectivities differ in distinct temperature ranges, caused by competition among reaction and product desorption steps. Sensitivity analysis shows which elementary steps significantly affect the overall benzoic acid hydrogenation activity and selectivity.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1244-1258"},"PeriodicalIF":3.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00561a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148238","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}

{"title":"Enantioselective synthesis of (R)-citronellal from geraniol with an immobilised copper alcohol oxidase and ene reductase†","authors":"Beatrice Tagliabue, Christian M. Heckmann, Rocio Villa, Sacha Grisel, Jean-Guy Berrin, Mickael Lafond, David Ribeaucourt and Caroline E. Paul","doi":"10.1039/D5RE00034C","DOIUrl":"10.1039/D5RE00034C","url":null,"abstract":"<p >(<em>R</em>)-Citronellal is one of the key chiral intermediates in the synthesis of the isomer (−)-menthol, one of the most commercialised terpenoid flavours worldwide. Enzymatic approaches could represent a less energy-demanding alternative for its synthesis, such as a previously reported bienzymatic cascade starting from inexpensive, commercially available geraniol. A copper radical oxidase (<em>Cgr</em>AlcOx) followed by a flavin-dependent ene reductase (OYE2) were used to obtain (<em>R</em>)-citronellal. Here, we used a metal-affinity immobilisation strategy on the His-tagged enzymes for the cascade and studied enzyme recovery and reusability as well as increased solvent tolerance. After screening a panel of resins for enzyme immobilisation and water-immiscible co-solvents, we successfully obtained 95% conversion to (<em>R</em>)-citronellal with 96.9% enantiomeric excess (ee) in a concurrent cascade after 7 h of reaction time, starting from 10 mM of geraniol.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1320-1325"},"PeriodicalIF":3.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11908116/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143646383","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}

{"title":"State-of-the-art heterogeneous polymerization kinetic modelling processes and their applications","authors":"Shu-Cen Lai, Jie Jin and Zheng-Hong Luo","doi":"10.1039/D5RE00005J","DOIUrl":"https://doi.org/10.1039/D5RE00005J","url":null,"abstract":"<p >Heterogeneous polymerization systems have been widely used in large-scale industrial production. Utilizing kinetic simulations to effectively reveal the underlying mechanisms of complex heterogeneous systems is invaluable for both product design and process optimization. The aim of this study is to comprehensively review the recent research progress on the development of heterogeneous polymerization kinetic modelling. We first provide an overview of the kinetic modelling processes of heterogeneous polymerization systems, focusing on mass transfer models, phase-state treatment approaches, and numerical methods. Further, to illustrate the importance of heterogeneous polymerization kinetic modelling, we give examples of its utilization in three research domains, including understanding the kinetics and transfer features, enabling the performance-oriented polymer structure design and precise synthesis, and guiding reactor design, optimization, and scale-up. Finally, the challenges and perspectives of heterogeneous polymerization kinetic modelling are discussed for future development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 942-952"},"PeriodicalIF":3.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re00005j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888507","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}

{"title":"Multi-scale decision-making of HRES-powered flexible microreaction electrosynthesis systems","authors":"Weigu Wen, Yueheng Han, Congqin Ge, Yuxuan Xu, Kai Wang and Zhihong Yuan","doi":"10.1039/D4RE00519H","DOIUrl":"https://doi.org/10.1039/D4RE00519H","url":null,"abstract":"<p >The imperative target of net-zero necessitates the energy-intensive chemical industry to adopt massive renewable energy to reduce emissions of greenhouse gases and pollutants. The inherent conflict between the intermittent renewable energy supply and the rigid energy demand of the chemical industry traditionally entails costly investment in excessive storage systems to guarantee operational stability, leading to a drastic increase in production costs. In contrast, we design a flexible microreaction electrosynthesis system (MESS) powered by hybrid renewable energy systems (HRES) to mitigate the rigidity of energy demand and to moderate the reliance on energy storage. Accordingly, a mixed-integer linear programming (MILP) model is introduced for the multi-scale decision-making on the configuration and operating conditions for producing high-value-added organic chemicals under variable solar and onshore wind energy supplies. We demonstrate that investment in energy storage systems can be reduced by up to 66.6% through flexible operations compared to traditional rigid chemical production. Comparisons highlight the rapid start-up and shut-down abilities of microreactors that enable MESS to accommodate renewable energy variability. Furthermore, we identify the main bottlenecks of the integrated MESS-HRES that hinder the overall performance: current densities, Faraday efficiencies and microreactor costs at the unit level, and costs and variations of solar energy at the system level.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1302-1319"},"PeriodicalIF":3.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148243","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}

{"title":"Optimization of low-temperature pyrolysis of dioxins in fly ash from municipal solid waste incineration: adding catalysts and inhibitors†","authors":"Zhuoyu Wen, Weishi Li, Li Li, Li Xiaoting, Dahai Yan and Yang Liao","doi":"10.1039/D4RE00592A","DOIUrl":"https://doi.org/10.1039/D4RE00592A","url":null,"abstract":"<p >This study simulates the low-temperature heat treatment of municipal solid waste incineration fly ash (MSWIFA, abbreviated as FA) under industrial conditions and investigates the enhancement of the process by inhibitors and catalysts. The results show that compared with the experimental group without catalysts or inhibitors, neither CaO nor CO(NH<small>₂</small>)<small>₂</small> can play an optimization role. Among the inhibitors, the total concentration and toxicity of dioxins in the 10 wt% CaO experimental group are the lowest, which are 467.01 ± 57.55 ng kg<small>⁻¹</small> and 48.40 ± 8.40 ng I-TEQ per kg, respectively. Among the two catalysts (MnO and V<small>₂</small>O<small>₅</small>), the experimental group with 1 wt% MnO has the best degradation efficiency. The total concentration and toxicity of dioxins in FA are 371.58 ± 19.92 ng kg<small>⁻¹</small> and 34.45 ± 2.56 ng I-TEQ per kg, respectively, and the removal rate and detoxification rate are 96.64% and 95.58%. These values meet the requirements of “China's Technical Specification for Pollution Control of Fly Ash from Domestic Waste Incineration” (trial) (HJ 1134-2020, China). XRD and FT-IR analyses indicate that dioxin degradation is likely due to dioxins being adsorbed onto the surface of MnO. Furthermore, the presence of manganese encourages the creation of radicals and oxidative ring opening, leading to carbonate formation. Simultaneously, dechlorination and substitution reactions take place, with Cl substitution on the benzene ring resulting in the production of Cl<small>₂</small> and HCl. Therefore, promoting the degradation of dioxins is more feasible than inhibiting the synthesis of dioxins. This study provides a new way to realize low-temperature heat treatment of dioxins in domestic waste incineration facilities.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1337-1349"},"PeriodicalIF":3.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148227","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}

{"title":"Rapid and efficient removal of Sr2+ ions by the easy-to-operate and environmentally friendly KInSnS4@collagen fiber aerogel†","authors":"Jiang-Hai He, Jun-Hao Tang, Ming-Dong Zhang, Chuan Lv, Lu Yang, Zhi-Hua Chen, Yi Liu, Hai-Yan Sun, Mei-Ling Feng and Xiao-Ying Huang","doi":"10.1039/D4RE00545G","DOIUrl":"https://doi.org/10.1039/D4RE00545G","url":null,"abstract":"<p >It is still a challenge to capture radioactive <small>⁹⁰</small>Sr<small>²⁺</small> ions conveniently, quickly, and efficiently from complex aqueous solutions. Herein, a composite material, KInSnS<small>₄</small>@CF aerogel (CF = collagen fiber), was prepared by loading the metal sulfide ion exchanger KInSnS<small>₄</small> on collagen fibers through electrostatic self-assembly. The KInSnS<small>₄</small>@CF aerogel is well shaped and maneuverable. It can efficiently capture Sr<small>²⁺</small> with satisfactory adsorption capacity (<em>q</em><small>^Sr</small><small>_max</small> = 41.48 mg g<small>⁻¹</small>), fast kinetics (adsorption equilibrium within 2 min), broad pH activity (pH = 2–12), and facile elution. The aerogel shows good selectivity for the capture of Sr<small>²⁺</small> under the coexistence of Na<small>⁺</small>, Cs<small>⁺</small>, Ca<small>²⁺</small>, and Mg<small>²⁺</small>, as well as in actual water samples. In addition, it can serve as the stationary phase being used in the ion exchange column for the efficient treatment of Sr<small>²⁺</small> solutions in a dynamic manner. The efficient Sr<small>²⁺</small> removal of the KInSnS<small>₄</small>@CF aerogel mainly originates from ion exchange between Sr<small>²⁺</small> and K<small>⁺</small> in the interlayer spaces of KInSnS<small>₄</small>, while the CFs mainly serve as support materials. This work not only provides a new easy-to-operate and environmentally friendly metal sulfide composite aerogel, but also paves the avenue for the application of CFs from leather industry waste.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1173-1183"},"PeriodicalIF":3.4,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888506","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}