Reaction Chemistry & Engineering最新文献

{"title":"Mechanistic insights into C–O bond cleavage in erythritol during hydrodeoxygenation on an Ir–ReOx catalyst†","authors":"Ajin Rajan and Jithin John Varghese","doi":"10.1039/D4RE00245H","DOIUrl":"10.1039/D4RE00245H","url":null,"abstract":"<p >1,4-Butanediol (1,4-BDO) is a key ingredient in the polymer industry. When derived from renewable erythritol, it can pave the way for sustainable poly(butylene terephthalate), polyurethane and polyester manufacturing. Hydrodeoxygenation (HDO) of erythritol on Brønsted acidic metal–metal oxide catalysts can result in 1,4-BDO, among other alcohols. Selective synthesis of 1,4-BDO requires deep insights into the preference for the cleavage of the different C–O bonds and the energy landscape for the formation of other polyol intermediates. In this work, we used density functional theory (DFT) simulations to investigate HDO of erythritol and other polyol intermediates on an inverse Ir–ReO<small>_<em>x</em></small> catalyst, where rhenium oxide is dispersed on iridium. While Ir nanoparticles can drive HDO through dehydroxylation, a protonation and dehydration mechanism happening at the Ir–ReO<small>_<em>x</em></small> interface has greater kinetic relevance. We show the kinetic preference for secondary C–O cleavage in erythritol to explain the predominant formation of 1,2,4-butanetriol (1,2,4-BTO) during erythritol HDO. The kinetic preference for 1,4-BDO formation from 1,2,4-BTO makes it the most prominent butanediol during erythritol HDO. C–O bond cleavage in 1,4-BDO has a high barrier making 1,4-BDO less reactive in a polyol mixture. This indicates potential selective formation of 1,4-BDO, with a possibility of tuning reaction conditions and reaction time to maximise its yield. Our analyses reveal that C–O cleavage is not always the kinetically relevant step and it can be the hydrogenation that follows the C–O cleavage. Hence, reactions at high hydrogen pressure and lower temperatures might suit higher selectivity towards desired alcohols such as 1,4-BDO.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 1","pages":" 27-37"},"PeriodicalIF":3.4,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141780870","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-inline extraction of polar co-solvent during sequential flow reactions†","authors":"Kwihwan Kobayashi, Jun Matsuzawa, Hajime Kawanami and Nagatoshi Koumura","doi":"10.1039/D4RE00276H","DOIUrl":"10.1039/D4RE00276H","url":null,"abstract":"<p >The development of multistep flow synthesis methods for fine chemicals and pharmaceuticals is desirable in terms of cost and energy efficiency. Methods for connecting the first and second flow reactions are essential for the development of multistep flow reactions; however, some reactions are incompatible with necessary solvents. Herein, we developed continuous-removal methods for polar co-solvents that negatively affect subsequent reactions. These sequential flow reactions facilitated the production of multicomponent compounds from simple starting materials. Furthermore, scaled-up experiments for the sequential flow reaction using reaction columns approximately 40 times larger than the original were successfully conducted, with a productivity of 16.1 g h<small>⁻¹</small>. We believe that our continuous extraction method holds promise for various sequential flow reactions for the synthesis of fine chemicals and pharmaceuticals.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3116-3121"},"PeriodicalIF":3.4,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754065","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":"Engineering the grain boundary and surface sites of binary Cu–Mn catalysts to boost CO oxidation†","authors":"Xiangxue Zhang, Xinyi Chao, Nina Fei, Wenyao Chen, Gang Qian, Jing Zhang, De Chen, Xuezhi Duan, Xinggui Zhou and Weikang Yuan","doi":"10.1039/D4RE00222A","DOIUrl":"10.1039/D4RE00222A","url":null,"abstract":"<p >The catalytic oxidation of CO over Cu-based catalysts has garnered significant interest due to their promising potential in addressing environmental pollution and enhancing industrial processes. Herein, we report a dual-stimuli strategy to boost the catalytic performance of CO oxidation <em>via</em> synergistically harnessing active Cu<small>⁺</small> species with oxygen vacancies by engineering the grain boundary of Cu–Mn catalysts. Nanorod-like MnO<small>₂</small> with a tunnel structure was prepared by a hydrothermal method and employed as the catalyst support, where different amounts of Cu were further introduced <em>via</em> impregnation to obtain Cu/MnO<small>₂</small> catalysts. It is found that apart from the highly dispersed Cu species within the MnO<small>₂</small> lattice to create lattice mismatch and distortion, some Cu are present as oxidized nanoparticles over the MnO<small>₂</small> surface, thus sparking off increased dislocations and grain boundaries. A combination of characterization methods demonstrates that the proportion of active Cu<small>⁺</small> species decreases with increasing amount of Cu, presenting an inverse relationship to the abundance of oxygen vacancies over the catalyst surface. Correspondingly, both Cu<small>⁺</small> species and oxygen vacancies are identified as the main active sites for the adsorption and activation of CO and O<small>₂</small>, respectively. Therefore, a trade-off between the percentage of active Cu<small>⁺</small> species and oxygen vacancies for the 15% Cu/MnO<small>₂</small> catalyst with a moderate Cu introduction contributes to its highest catalytic activity, with <em>T</em><small>₅₀</small> and <em>T</em><small>₉₀</small> reaching 66 °C and 89 °C, respectively. This investigation highlights the potential of synergistically harnessing active Cu<small>⁺</small> species with oxygen vacancies <em>via</em> grain boundary engineering for enhanced catalytic performance in CO oxidation applications.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2659-2668"},"PeriodicalIF":3.4,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745390","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":"Extraction by ionic liquids for the case of detoxification of lignocellulosic hydrolysates","authors":"Konstantza Tonova, Svetlana Zhivkova, Madlena Lazarova and Ahmad Mustafa","doi":"10.1039/D4RE00154K","DOIUrl":"10.1039/D4RE00154K","url":null,"abstract":"<p >This study deals with hydrophobic phosphonium ionic liquids (ILs), phosphinate and neodecanoate, used in liquid–liquid extraction for the purpose of complex detoxification of lignocellulosic hydrolysates from inhibitors, whilst preserving the sugar content. The topic is considered from two aspects, a theoretical one in which extraction from a model multicomponent solution composed of acids, furan, phenolics, and sugars is investigated, and practically by employing a real rice straw hydrolysate. Using the model solution in cross-current extraction mode, the main process parameters, pH and concentration of the ILs, are studied. The extraction mechanisms of acids (sulfuric, gallic, acetic and levulinic acids) and aldehydes (vanillin and furfural) are established. Extraction of the acids in both ILs proceeds by a competitive mechanism until the two reactive H-bonding sites located at the two oxygen atoms in the IL's anion are occupied. In addition to H-bonding, extraction of the phenolic acid is substantially assisted by hydrophobic interactions, while the sulfuric acid is readily extracted by protonation of the IL's anion. An above-stoichiometric extraction of acids by phosphonium phosphinate has been found, which occurs by acid–acid H-bonds between phenolic and organic acids. Co-extraction between phenolic acid and phenolic and furanic aldehydes is observed which is based on the H-bonds that exist in acidic media and the staking interactions of the aromatic rings. The extraction of real rice straw hydrolysate carried out in three runs reaches a high removal of organic acids (over 63%), furans (over 80%) and phenolic compounds (over 97%) in each run.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2610-2622"},"PeriodicalIF":3.4,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141722384","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":"Outstanding Reviewers for Reaction Chemistry & Engineering in 2023","authors":"","doi":"10.1039/D4RE90019G","DOIUrl":"10.1039/D4RE90019G","url":null,"abstract":"<p >We would like to take this opportunity to thank all of <em>Reaction Chemistry &amp; Engineering</em>'s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>Reaction Chemistry &amp; Engineering</em> in 2023.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 1993-1993"},"PeriodicalIF":3.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141611885","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":"Unveiling the dual-function applications of a magnetically retrievable chemically grafted Schiff base Cu-complex on graphene oxide for catalytic and antibacterial applications†","authors":"Himadri Priya Gogoi, Nilotpal Goswami and Pranjit Barman","doi":"10.1039/D4RE00211C","DOIUrl":"10.1039/D4RE00211C","url":null,"abstract":"<p >In the current work, a new Schiff base complex containing Cu(<small>II</small>) ions was covalently anchored in a stepwise manner onto graphene oxide nanosheets, followed by a combination with magnetic iron oxide, to form a potential catalyst for C–H functionalization of indoles on C-3 <em>via</em> a one-pot multicomponent reaction. Numerous methods were used to characterize the as-synthesized nanostructure (CuSB-GO/FO), including VSM, XRD, FT-IR, SEM, EDX, TEM, Raman spectroscopy, N<small>₂</small> adsorption–desorption measurement and ICP-AES techniques. The as-synthesized CuSB-GO/FO was evaluated as an effective and versatile catalyst for reactions of different indoles, malononitrile, and substituted benzaldehydes in ethanol/water at 35 °C, producing 3-substituted indoles. The key advantages of this catalytic system are its quick reaction time, high product yield, use of green solvents, and ease of separation. The catalytic efficiency of the nanocatalyst rose dramatically when the complex was covalently grafted onto the graphene oxide surface, which might be due to the chemical alteration of the graphene oxide sheets. The findings demonstrate that the synthesized nanocatalyst may be reused four times with great chemical stability and minimal reduction in its activity as a catalyst. In addition, Gram-positive and Gram-negative bacteria responded well to the synthesized nanostructure as an antibacterial agent.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2569-2583"},"PeriodicalIF":3.4,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573545","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":"Lipase-catalysed esterification in a reactive natural deep eutectic solvent leads to lauroylcholine chloride rather than glucose ester†","authors":"Alina Ramona Buzatu, Miguel Angel Soler, Ozge Ozkilinc, Sara Fortuna, Diana Maria Dreavă, Ioan Bîtcan, Paolo Giannozzi, Federico Fogolari, Lucia Gardossi, Francisc Peter, Anamaria Todea and Carmen Gabriela Boeriu","doi":"10.1039/D4RE00209A","DOIUrl":"10.1039/D4RE00209A","url":null,"abstract":"<p >Enzymatic esterification of glucose with lauric acid catalyzed by lipase B from <em>Candida antarctica</em> immobilized on acrylic resin (LAR) was investigated in hydrophilic reactive natural deep eutectic solvents (R-NADESs), composed of choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and glucose (Glc) and water as hydrogen bond donors (HBDs) in different molar ratios. Surprisingly, no glucose esters were obtained, the only esterification product being lauroylcholine chloride, obtained in the ChCl : Glc : H<small>₂</small>O (2 : 1 : 1) ternary R-NADES. Molecular dynamic simulations clearly explained this unexpected selectivity, showing that the lipase-catalyzed synthesis of glucose lauryl esters is hindered by the manifold and strong interactions in the H-bond network and the formation of voluminous adducts of glucose with the chloride ion, which cannot access the alcohol catalytic subsite. The free choline chloride, not involved in the H-bond network of the ChCl : Glc : H<small>₂</small>O (2 : 1 : 1) R-NADES, did enter the CalB catalytic pocket and was converted to the corresponding lauroylcholine ester.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2623-2634"},"PeriodicalIF":3.4,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00209a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573547","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":"Biocatalysis in microfluidic systems: an experimental basis for data science†","authors":"John M. Woodley","doi":"10.1039/D3RE00703K","DOIUrl":"10.1039/D3RE00703K","url":null,"abstract":"<p >Biocatalysis using (recombinant) enzymes is gaining traction as a method for selective chemical catalysis, especially in the pharmaceutical industry. Flow systems, especially miniaturized microfluidic systems, have proven to be a useful method to test new enzyme reaction sequences and processes. In this brief article, it will be argued that microfluidics not only can be used for rapid testing of reaction processes, but also can be used nowadays for collection of process data, especially for parameters in relevant kinetic and stability models, and thereby to help with scale-up, which remains a major challenge for implementation of biocatalysis in many industries. The ability to quickly change conditions (such as temperature) in microfluidic devices makes them ideally suited to such scale-down studies, and can form the experimental basis for data science as a tool for future process development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 2028-2033"},"PeriodicalIF":3.4,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573546","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":"Selective hydrogenation of CO2 to formic acid with higher yield in an aqueous medium with a nano-nickel-metal catalyst: reaction parameter optimization by response surface methodology (RSM)†","authors":"Rajeev Ranjan, Prakash Biswas and K. K. Pant","doi":"10.1039/D4RE00194J","DOIUrl":"10.1039/D4RE00194J","url":null,"abstract":"<p >A highly active mesoporous nano-nickel catalyst was synthesized by the sol–gel method for the selective conversion of CO<small>₂</small> to formic acid (FA) in an aqueous medium. In this study, CO<small>₂</small> hydrogenation reactions were performed in a high-pressure autoclave, and the experimental conditions were set by using the response surface methodology (RSM). The RSM analysis was done using a three-factor, one-response, and five-level central composite design (CCD) integrated with the desirability approach. Experiments revealed that under the optimized reaction conditions (200 °C, 60 bar), the obtained formic acid yield was significantly high (2245 μmol g<small>⁻¹</small> h<small>⁻¹</small>) with 100% catalyst selectivity. The obtained turnover number (TON) was ∼285, significantly higher in an aqueous medium and the presence of a non-noble nickel nano-metal catalyst. Mesoporous nano nickel particles (15–26 nm) facilitated the selective adsorption and splitting of hydrogen molecules to hydrogen radicals, which further reacted with the carbonate ions present in the reaction medium. Na<small>₂</small>CO<small>₃</small> acted as a promoter, which enhanced the CO<small>₂</small> adsorption and the formic acid yield. The catalyst recyclability was confirmed by performing the experiments five times and a constant yield of formic acid was found.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2635-2646"},"PeriodicalIF":3.4,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141577931","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":"Intelligent method for analysis of the active phase of hydrogenation catalysts: stripe phase identification of UC-S/SC-S†","authors":"Zhujun Wang, Ailin Cui and Song Bao","doi":"10.1039/D4RE00239C","DOIUrl":"10.1039/D4RE00239C","url":null,"abstract":"<p >In order to realize the intelligent recognition and statistics of hydrogenation catalyst image information, different from traditional methods, this paper presents a new method to judge the active phase by image recognition. Firstly, image enhancement and Gabor filtering are used for image preprocessing to suppress the background and obtain the region with strong contrast. The fringe of the hydrogenation catalyst was extracted using a morphological algorithm. Finally, the edge of the fringe was extracted using a Sobel operator to detect the end of the skeleton line, which realized segmentation and recognition of the hydrogenation catalyst image. This method extracts features through data analysis of a large number of image samples to improve the robustness of the method and reduce the errors caused by manual judgment. The experimental results show that the proposed method has high accuracy and is highly consistent with the traditional method of judging the active phase, which has practical engineering application value.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2647-2658"},"PeriodicalIF":3.4,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573548","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}