Reaction Chemistry & Engineering最新文献

{"title":"Intrinsic microkinetic effects of spray-drying and SiC co-support on Mn–Na2WO4/SiO2 catalysts used in oxidative coupling of methane†","authors":"Gontzal Lezcano, Shekhar R. Kulkarni, Vijay K. Velisoju, Natalia Realpe and Pedro Castaño","doi":"10.1039/D4RE00403E","DOIUrl":"https://doi.org/10.1039/D4RE00403E","url":null,"abstract":"<p >This paper presents a microkinetic model to evaluate the effects of a silicon carbide (SiC) co-support and the shaping method on Mn–Na<small>₂</small>WO<small>₄</small>/SiO<small>₂</small> catalysts used for the oxidative coupling of methane. The model considers mass transfer, catalytic, and gas-phase kinetics, and it is trained with experimental values (product composition) of three Mn–Na<small>₂</small>WO<small>₄</small> catalysts for calculating the kinetic parameters using catalytic descriptors while maintaining thermodynamic consistency. The catalysts were an SiO<small>₂</small>-supported catalyst prepared through impregnation and two SiO<small>₂</small>–SiC-supported catalysts (with βSiC and α + βSiC) prepared <em>via</em> spray-drying. Our analysis shows how the type of SiC and preparation method affect the textural properties and result in distinct CH<small>₃</small>˙ radical oxidation, HO<small>₂</small>˙ quenching, C<small>₂</small>H<small>₄</small> oxidation, and CO<small>_<em>X</em></small> transformation pathways, eventually leading to CH<small>₄</small> conversion and C<small>₂</small> selectivity. Our approach facilitates the assessment of the effects of the promoter and support on individual and global reaction networks.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 975-998"},"PeriodicalIF":3.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00403e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888512","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":"Sulphidation of Cu2+, CuO and Cu2O within the matrix of carboxylic cation exchangers – compositional, morphological and thermal properties of CuxS containing composites","authors":"Elżbieta Kociołek-Balawejder, Irena Jacukowicz-Sobala, Juliusz Winiarski, Igor Mucha and Katarzyna Winiarska","doi":"10.1039/D4RE00604F","DOIUrl":"https://doi.org/10.1039/D4RE00604F","url":null,"abstract":"<p >The study aimed to optimize the synthesis of novel hybrid ion exchangers and evaluate the dispersion of copper sulphides within the porous polymeric phase. Cu<small>_<em>x</em></small>S fine particles were embedded within carboxylic cation exchangers (CCEs) using different copper precursors: Cu<small>²⁺</small> connected with functional groups (a), dispersed CuO particles (b), and dispersed Cu<small>₂</small>O particles (c). The study evaluated the impact of the CCEs' structure (gel-type or macroporous) and the copper precursor (Cu<small>²⁺</small>, CuO, or Cu<small>₂</small>O) on the quantity, chemical composition, distribution and morphology of Cu<small>_<em>x</em></small>S. After sulphidation Cu<small>_<em>x</em></small>S rich HIXs containing as much as 15.3–12.0 wt% Cu and 5.97–3.16 wt% S were prepared. XRD analysis indicated CuS, Cu<small>₄</small>S<small>₇</small>, Cu<small>_1.75</small>S, Cu<small>_1.95</small>S, and Cu<small>₂</small>S phase inside the beads, with covellite (a), (b), and chalcocite (c) as the main crystalline phase. The XPS analyses revealed the products of Cu<small>_<em>x</em></small>S oxidation and hydrolysis: CuO, Cu(OH)<small>₂</small>, and CuSO<small>₄</small> on the surface of the CCE grains. In the HIXs, the deposit was dispersed evenly throughout the volume of the beads. The deposit resulting from (a) and (b) was nanometric, without the formation of large agglomerates. The deposit resulting from (c) was characterized by much larger sizes exceeding several hundred nanometers. The TG/DTG curves of four HIXs obtained by the (b) and (c) transformation showed remarkable thermal stability up to a temperature of 400 °C. The obtained composites, by combining the affinity, selectivity and exceptionally high sorption capacity of Cu<small>_<em>x</em></small>S for heavy metals (especially mercury) may be valuable in water purification processes in column flow-through systems.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1077-1095"},"PeriodicalIF":3.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888488","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":"Fast and scalable continuous flow synthesis of butenolides and coumarins†","authors":"Lucas Coral Ferreira, Renan de Souza Galaverna, Tom McBride, Rodrigo Costa e Silva, Duncan L. Browne and Julio Cezar Pastre","doi":"10.1039/D4RE00567H","DOIUrl":"https://doi.org/10.1039/D4RE00567H","url":null,"abstract":"<p >Herein, we present a versatile and efficient continuous flow protocol for the synthesis of structurally diverse butenolides and coumarins through the <em>in situ</em> generation of acylketenes <em>via</em> the retro hetero-Diels–Alder reaction of dioxinones with α-hydroxy-ketones and salicylaldehydes, respectively. This protocol enabled the synthesis of 5 examples of butenolides with yields ranging from 30 to 91% and 16 examples of coumarins with yields ranging from 30 to 99%. The versatility and practicality of the protocol were demonstrated by the gram-scale synthesis of a biologically relevant γ-spiro butenolide core, as well as the production of benzo-coumarins. Modern medicinal chemistry demands both scalability and the ability to synthesize structurally diverse compounds in a single synthetic platform, and our methodology effectively addresses these challenges in a fast and safer manner.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1108-1113"},"PeriodicalIF":3.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00567h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888490","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":"Hydrogenation of CO2 to synthetic natural gas (SNG) with 100% selectivity over a Ni–ZnO–MgO catalyst†","authors":"Mahendra Kumar Meena, Shalini Biswas and Prakash Biswas","doi":"10.1039/D4RE00587B","DOIUrl":"https://doi.org/10.1039/D4RE00587B","url":null,"abstract":"<p >The CO<small>₂</small> hydrogenation activity of a Ni–ZnO–MgO catalyst prepared by the co-precipitation technique is evaluated in a down-flow tubular reactor. The physicochemical properties of the catalyst were characterized by various techniques, including N<small>₂</small>-physisorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), hydrogen chemisorption, FE-SEM, TGA, TEM, XPS, <em>etc.</em> Hydrogenation experiments were performed at different temperatures (200–400 °C) and mild pressure (1–15 bar) at a constant feed gas (H<small>₂</small>/CO<small>₂</small>/N<small>₂</small>) molar ratio of 3 : 1 : 3. The total feed flow rate was maintained at 3 × 10<small>⁻³</small> mol min<small>⁻¹</small>. Results demonstrated that the Ni–ZnO–MgO catalyst was ∼100% selective to CH<small>₄</small>. ZnO helped to improve not only the catalyst stability <em>via</em> hydrogen spillover effect but also the nickel metal dispersion, and MgO enhanced the CO<small>₂</small> adsorption. Overall, the reaction mechanism followed the formate species pathway to obtain almost 100% methane selectivity. Time-on-stream study suggested that the catalyst was stable with negligible carbon formation. The used catalyst characterization results showed that the catalyst morphology remained unchanged before and after the reaction. Therefore, the developed Ni–ZnO–MgO catalyst is very promising for the selective hydrogenation of CO<small>₂</small> to synthetic natural gas (SNG).</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1054-1066"},"PeriodicalIF":3.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888486","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":"An integrated strategy for corncob pretreatment and coproduction of furfural and monosaccharides based on p-toluenesulfonic acid and a deep eutectic solvent system†","authors":"Liping Luo, Wenxuan Wu, Yanan Shen, Yuheng Tao, Liqun Wang and Qing Qing","doi":"10.1039/D4RE00500G","DOIUrl":"https://doi.org/10.1039/D4RE00500G","url":null,"abstract":"<p >High-value valorization of cellulose and hemicellulose fractions in lignocellulosic biomass is crucial for a feasible biomass refinery scheme. In this study, an integrated strategy was developed for pretreatment of corncob and coproduction of furfural and high-concentration fermentable sugars. The hemicellulose fraction in raw corncob was selectively extracted to produce a xylose-rich hydrolysate <em>via</em> pretreatment with dilute <em>p</em>-toluenesulfonic acid (<em>p</em>-TsOH) under optimal reaction conditions (0.5% <em>p</em>-TsOH, 160 °C, and 30 min). Thereafter, the xylose hydrolysate was subjected to catalytic conversion in a DES (TEBAC : LA = 1 : 4) system at 190 °C for 10 min. Notably, 78.6% furfural yield was achieved, and the corresponding xylose conversion was close to 100.0%. In addition, the pretreated corncob residue exhibited excellent enzymatic digestibility as the yields of reducing sugar and glucose were 90.7% and 97.0%, respectively, at a high solid loading of 12%. This proposed approach represents an integrated strategy for coproduction of multiple products from agriculture residues.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1096-1107"},"PeriodicalIF":3.4,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888489","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":"Correction: Intensification of silver nanoparticle synthesis through continuous flow split and recombine microreactors","authors":"Amritendu Bhuson Ghosh, Rakesh Kumar and Arnab Atta","doi":"10.1039/D5RE90004B","DOIUrl":"https://doi.org/10.1039/D5RE90004B","url":null,"abstract":"<p >Correction for ‘Intensification of silver nanoparticle synthesis through continuous flow split and recombine microreactors’ by Amritendu Bhuson Ghosh <em>et al.</em>, <em>React. Chem. Eng.</em>, 2024, <strong>9</strong>, 1707–1720, https://doi.org/10.1039/D4RE00025K.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 721-721"},"PeriodicalIF":3.4,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re90004b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489302","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":"Correction: Rare-earth doped hexagonal NaYbF4 nanoprobes with size-controlled and NIR-II emission for multifunctional applications","authors":"Yu Min, Xin Ding, Bing Yu, Hailin Cong and Youqing Shen","doi":"10.1039/D5RE90005K","DOIUrl":"https://doi.org/10.1039/D5RE90005K","url":null,"abstract":"<p >Correction for ‘Rare-earth doped hexagonal NaYbF<small>₄</small> nanoprobes with size-controlled and NIR-II emission for multifunctional applications’ by Yu Min <em>et al.</em>, <em>React. Chem. Eng.</em>, 2023, <strong>8</strong>, 2258–2269, https://doi.org/10.1039/D3RE00168G.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 719-720"},"PeriodicalIF":3.4,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re90005k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489301","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":"Modification of acidic groups over zeolites via calcination for the selective catalytic transformation of 2,3-butanediol in ethylene glycol","authors":"Shuo Ai, Kaili Gao, Zhenhua Huang, Linghui Liu and Wanguo Yu","doi":"10.1039/D4RE00278D","DOIUrl":"https://doi.org/10.1039/D4RE00278D","url":null,"abstract":"<p >Biomass and bio-derived chemicals can be transformed into ethylene glycol (EG) <em>via</em> catalytic hydrogenation, but a small amount of 2,3-butanediol (23BDO) is generated. 23BDO in EG was removed <em>via</em> the dehydration reaction over H-beta zeolite calcined at 800 °C, with a 23BDO conversion of 80.4% and corresponding SF value of 17.1, which was almost thrice that over the original zeolite due to the suppression of ketalization and oligomerization reactions of EG, especially the latter. The conversions of C<small>_3–6</small> diols depended on the numbers of carbon atoms due to a positive effect of the alkyl group on their reactivity, with five-fold SF values compared to the pristine zeolite. The pore and crystal structures of the zeolite were disturbed to a small extent after calcination, resulting in its weakened catalytic activity. The NH<small>₃</small>-TPD result proved that the number of acid sites was significantly reduced after calcination, and the ratios of medium and strong acid sites were slightly decreased. The thermal decomposition of Si(OH)Al (Brønsted acid) and EFAL groups (Lewis acid) was confirmed by FTIR. The order of the EG oligomerization reaction with respect to catalyst dosage (third order) was higher than that of the ketalization reaction (first order), so the decrease of the number of acid sites was most unfavorable to EG oligomerization. Compared to the ketalization reaction, the dehydration reaction of 23BDO was less affected after the elimination of EFAL groups, which could not catalyze the dehydration reaction. The used catalyst was regenerated by calcination at 600 °C. The conversions of 23BDO and EG declined to a small and similar degree in the reuse experiment, indicative of the high stability of this modified catalyst.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1067-1076"},"PeriodicalIF":3.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888487","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":"Vapor phase coupling of n-butanol over the mixed catalyst system PdZn/SiO2 + TiO2†","authors":"Evan C. Wegener","doi":"10.1039/D4RE00474D","DOIUrl":"https://doi.org/10.1039/D4RE00474D","url":null,"abstract":"<p >Coupling fermentation derived oxygenates <em>via</em> Guerbet-type reactions offers a potential route for producing fuels and chemicals from agricultural feedstocks. In this work the vapor phase reactions of <em>n</em>-butanol over a bimetallic PdZn/SiO<small>₂</small> catalyst and physical mixtures of PdZn/SiO<small>₂</small> and TiO<small>₂</small> were studied. The bimetallic catalyst was highly selective for n-butanol dehydrogenation without the subsequent decarbonylation of butanal which is characteristic of monometallic Pd nanoparticles. When combined with TiO<small>₂</small>, a known aldol condensation catalyst, the bifunctional system performs Guerbet-type coupling reactions and produces mixtures of C<small>₈</small> oxygenates and higher-order products including C<small>₇</small>, C<small>₈</small>, and C<small>₁₂</small> hydrocarbons. Results show that within the reaction network PdZn/SiO<small>₂</small> performs dehydrogenation/hydrogenation reactions and decarbonylates C<small>₈</small> aldehydes to form C<small>₇</small> hydrocarbons. TiO<small>₂</small> catalyzes aldol condensation and alcohol dehydration reactions responsible for producing C<small>₈</small> and C<small>₁₂</small> hydrocarbons. Based on the developed understanding of the function of each catalyst, it was shown that increasing the Brønsted acidity of the TiO<small>₂</small> catalyst resulted in an increase in the production of C<small>₈</small> hydrocarbons relative to C<small>₁₂</small> hydrocarbons. This work demonstrates the ability of bimetallic Pd-based catalysts that are selective for alcohol dehydrogenation to participate in Guerbet-type coupling reactions and that their combination with an appropriate aldol condensation/dehydration catalyst is an effective strategy to produce higher molecular weight oxygenates and hydrocarbons from renewable resources.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 906-916"},"PeriodicalIF":3.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698410","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":"Superior photocatalytic activity of Mn vanadate/reduced graphene oxide magnetic nanocomposite for the oxidation of methylene blue dye under sunlight irradiation†","authors":"Fatemeh Rahmatpour and Niaz Monadi","doi":"10.1039/D4RE00314D","DOIUrl":"https://doi.org/10.1039/D4RE00314D","url":null,"abstract":"<p >A magnetic photocatalyst based on reduced graphene oxide and semiconducting MnV<small>₂</small>O<small>₆</small> (rGO/Fe<small>₃</small>O<small>₄</small>/MnV<small>₂</small>O<small>₆</small>) was synthesized by magnetizing the rGO/MnV<small>₂</small>O<small>₆</small> composite for the efficient degradation of methylene blue (MB), a biodegradation-resistant dye. The prepared magnetic photocatalyst was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, Brunauer–Emmett–Teller surface area analysis, Barrett–Joyner–Halenda (BET-BJH) pore analysis and vibrating sample magnetometry (VSM). Its photocatalytic properties and activity were investigated using UV–Vis diffuse reflectance spectroscopy (DRS), fluorescence spectroscopy and inductively-coupled plasma analysis. The synthesized rGO/Fe<small>₃</small>O<small>₄</small>/MnV<small>₂</small>O<small>₆</small> nanocomposite exhibited a bandgap of 2.59 eV and a specific surface area of 201.5 m<small>²</small> g<small>⁻¹</small>. The optimum photocatalytic conditions for efficient MB photodegradation were determined, and the photocatalytic efficiency was investigated under different light irradiations, including blue and yellow light as well as sunlight. The rGO/Fe<small>₃</small>O<small>₄</small>/MnV<small>₂</small>O<small>₆</small> photocatalyst demonstrated excellent MB degradation efficiency, achieving up to 94% under sunlight irradiation. Additionally, the catalyst exhibited remarkable reusability, maintaining 88% degradation efficiency after the 6th cycle, with negligible structural changes. The magnetic properties of the employed photocatalyst played a key role in facilitating their separation and recycling. The kinetics and mechanism of the photodegradation process were evaluated, revealing a pseudo-first-order rate constant of 0.0882 min<small>⁻¹</small> for a hydroxyl radical-based mechanism. The MB degradation was driven by the generation of superoxide (O<small>₂</small>˙<small>⁻</small>) and hydroxyl (˙OH) free radicals during the reaction.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 876-893"},"PeriodicalIF":3.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698408","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}