Reaction Chemistry & Engineering最新文献

{"title":"Selective C–H functionalizations of arenes catalyzed by poly NHC–Pd in flow†","authors":"Shiqi Huang, Runqi Hao, Qiao Li, Li Wan and Fener Chen","doi":"10.1039/D4RE00140K","DOIUrl":"https://doi.org/10.1039/D4RE00140K","url":null,"abstract":"<p >A series of heterogenized NHC–Pd catalysts were developed to address the high economic cost of C<small>–</small>H functionalizations resulting from the poor recyclability of transition metal catalysts. The catalytic activities of the obtained solid hypercrosslinked catalysts were studied in C<small>–</small>H acetoxylation, iodination, and nitrosation.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 7","pages":" 1641-1645"},"PeriodicalIF":3.4,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453533","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":"Autonomous closed-loop photochemical reaction optimization for the synthesis of various angiotensin II receptor blocker molecules†","authors":"Dnyaneshwar Aand, Abhilash Rana, Amirreza Mottafegh, Dong Pyo Kim and Ajay K. Singh","doi":"10.1039/D4RE00138A","DOIUrl":"10.1039/D4RE00138A","url":null,"abstract":"<p >Optimization is gaining huge attention in industries like pharmaceuticals, fine chemicals, and petrochemicals to maximize reaction yield, minimize waste, and improve process efficiency. Optimization is keeping pace with variations in multiple reaction conditions and sustaining a shift from laboratories to industries. Herein, we report an integrated continuous flow reactor platform with Bayesian optimization (BO)-assisted reaction optimization that can autonomously explore the optimal conditions for photochemical bromination reactions of biologically active sartan intermediates. Further, the controlled optimized parameter is extended towards the efficient solar light utility for bromination reactions, and the reaction is achieved in a residence time of 32 sec with an excellent space–time yield of 7 kg L<small>⁻¹</small> h<small>⁻¹</small>. The individual photobromination and nucleophilic substitution steps for sartan intermediate synthesis smoothly transitioned from the mg h<small>⁻¹</small> to kg h<small>⁻¹</small> production. In addition, autonomously explored bromination conditions are integrated with continuous flow tools for synthesizing, extracting, and purifying the angiotensin II receptor blocker intermediate within only 7.2 min.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2427-2435"},"PeriodicalIF":3.4,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530558","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":"A laboratory scale fast feedback characterization loop for optimizing coated catalysts for emission control†","authors":"Tim Delrieux, Shweta Sharma, Florian Maurer, Paolo Dolcet, Maximilian Lausch, Anna Zimina, Camilo Cárdenas, Patrick Lott, Maria Casapu, Thomas Lennon Sheppard and Jan-Dierk Grunwaldt","doi":"10.1039/D4RE00168K","DOIUrl":"10.1039/D4RE00168K","url":null,"abstract":"<p >Coating of structured substrates like ceramic honeycombs plays an important role in heterogenous gas-phase catalysis. This work aims at understanding the effects of different coating parameters on the activity of a noble metal-based oxidation catalyst by using a novel fast and non-invasive photo-based channel analysis approach. The impact of the milling intensity, binder amount, catalyst layer thickness and distribution in the ceramic cordierite channels were systematically correlated with the activity profiles for CO, methane and propylene oxidation over a 1.8% Pd/Al<small>₂</small>O<small>₃</small> catalyst. High milling intensities led to the formation of thinner catalyst layers with smaller particles, which were more evenly distributed throughout all channels and allowed the reactants to penetrate more efficiently. In contrast, the amount of binder added had a negligible influence on the catalyst activity. These findings were validated by X-ray tomography and complemented by SEM-analysis, a diffuse backlight-illumination imaging method, and mercury intrusion porosimetry.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2868-2881"},"PeriodicalIF":3.4,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00168k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141253188","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":"Expanding analytical horizons: 3D HPLC calibration surfaces for micromole scale self-optimizing flow reactors†","authors":"Maëva Vallet, Daniel Cortés-Borda and François-Xavier Felpin","doi":"10.1039/D3RE00559C","DOIUrl":"10.1039/D3RE00559C","url":null,"abstract":"<p >In this paper, we use the concept of the HPLC 3D calibration surface for evaluating reaction performance in micromole scale self-optimizing flow systems. This approach enables comparing the analyte and internal standard relative levels for a wide range of internal standard concentrations. This approach considers fluctuations in response factors and potential nonlinearities in the Beer–Lambert law, which arise from performing HPLC analyses at different concentration ranges. The concept is validated by constructing a calibration surface for a formal [3 + 3] cycloaddition. The robustness of the 3D calibration surface is assessed in an autonomous flow self-optimization in a non-steady-state regime, where a standard 2D calibration curve produces inconsistent results due to variable concentration HPLC injections.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 2262-2269"},"PeriodicalIF":3.4,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141253087","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":"Development of a solid-compatible continuous flow reactor for the paraformaldehyde slurry mediated α-hydroxymethylation of methyl vinyl ketone†","authors":"Bavo Vandekerckhove, Lise Van Coillie, Bert Metten, Thomas S. A. Heugebaert and Christian V. Stevens","doi":"10.1039/D4RE00220B","DOIUrl":"10.1039/D4RE00220B","url":null,"abstract":"<p >The α-hydroxymethylation reactions hold a significant position within the pharmaceutical industry due to their intriguing nature. Despite numerous reported methods, they often entail prolonged reaction times and moderate yields. Moreover, the prevalent use of aqueous formaldehyde restricts the applicability of this chemistry to water-compatible substrates. Gaseous formaldehyde remains largely avoided due to its toxicity, hazards, and requirement for substantial excess. Within this context, paraformaldehyde emerges as a promising alternative for the C1 building block, offering safety and ease of handling. Continuous flow methodology is employed to facilitate the <em>in situ</em> depolymerization of paraformaldehyde under optimized conditions, enabling direct utilization of the released formaldehyde gas. This research explores the use of a paraformaldehyde slurry in continuous flow for α-hydroxymethylation reactions, with methyl vinyl ketone serving as a proof-of-concept substrate. A solid-compatible continuous flow reactor was self-constructed and the hydroxymethylation of methyl vinyl ketone could successfully be optimised, resulting in a STY of 2040 kg h<small>⁻¹</small> m<small>⁻³</small>.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 2240-2248"},"PeriodicalIF":3.4,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00220b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141195366","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":"Insights into performances of magnetic and bio-based doped-nanohydroxyapatites as water decontamination agents","authors":"Maria Laura Tummino, Giuliana Magnacca, Monica Rigoletto, Mery Malandrino, Claudia Vineis and Enzo Laurenti","doi":"10.1039/D4RE00160E","DOIUrl":"10.1039/D4RE00160E","url":null,"abstract":"<p >Hydroxyapatite, a mineral from the apatite group, is widely distributed in living organisms and largely studied because of its many properties, including the adsorption of many different substances. In this work, two functionalized nanohydroxyapatites were synthesized starting from their precursors (calcium hydroxide and phosphoric acid) in the presence of Fe(<small>II</small>)/(<small>III</small>) ions and bio-based substances (BBS) isolated from green compost. The products were characterized with different techniques (nitrogen adsorption/desorption, ATR-FTIR, XRD, TGA and <em>ζ</em>-potential measurements) and compared to nanohydroxyapatite obtained without further functionalization. The ability of these materials to remove different water pollutants by adsorption was tested using two organic dyes (crystal violet and methyl orange) and four inorganic ions, Al(<small>III</small>), Cr(<small>III</small>), Ni(<small>II</small>) and As(<small>V</small>), characterized by different ionic charges, dimensions and nature. Moreover, for the same purpose, the antibacterial properties of iron- and iron/BBS-added materials were also tested. The result showed the effective adsorption capability of the materials, in particular with respect to crystal violet, Al(<small>III</small>) and Cr(<small>III</small>), and an enhancement of adsorption capacity with respect to all the adsorbates after functionalization. Finally, the tests towards <em>Staphylococcus aureus</em> and <em>Escherichia coli</em> showed high antimicrobial activity for the bare nanohydroxyapatite samples, whereas the doping with iron and BBS or the high-temperature treatment remarkably impacted this capacity depending on the bacterial strain to eliminate.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2321-2332"},"PeriodicalIF":3.4,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00160e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141195375","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":"Water-assisted ketonization of methyl palmitate to palmitone over metal incorporated TiO2 catalysts†","authors":"Jetsadagorn Pittayatornkul, Tosapol Maluangnont, Siriporn Jongpatiwut, Piyasan Praserthdam, Makoto Ogawa and Tawan Sooknoi","doi":"10.1039/D4RE00111G","DOIUrl":"10.1039/D4RE00111G","url":null,"abstract":"<p >Ketonization of methyl palmitate to palmitone, a bio-lube precursor, was investigated over noble metal (Pt, Ru, and Pd) incorporated TiO<small>₂</small> catalysts in the presence of water under an atmospheric H<small>₂</small>/N<small>₂</small> flow. Methyl palmitate underwent hydrolysis to palmitic acid that ketonized to palmitone over Lewis Ti<small>³⁺</small> sites. The water co-feeding also suppressed hydrodeoxygenation of methyl palmitate and palmitone cracking leading to high palmitone selectivity. The incorporated metals facilitated H<small>₂</small> dissociation/spillover on TiO<small>₂</small> which generated more Lewis Ti<small>³⁺</small> sites for higher ketonization activity. At 400 °C, 0.5Pd/TiO<small>₂</small> provided ∼90% conversion with &gt;85% palmitone selectivity and &gt;25 h stability, due to its efficient H<small>₂</small> dissociation/spillover to continually recover Lewis Ti<small>³⁺</small> sites. Meanwhile 0.5Pt/TiO<small>₂</small> promoted excessive hydrodeoxygenation, leading to the deactivation from CO poisoning at the metallic Pt sites. The findings of this study offer a sustainable approach for the selective production of bio-lube precursors from renewable fatty acid methyl esters.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2345-2357"},"PeriodicalIF":3.4,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141165586","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":"Molybdenum oxide with a varied valency ratio to enable selective d-galactose epimerization to d-talose†","authors":"Bhawana Devi, Senthil Murugan Arumugam, Ravi Kumar Kunchala, Paramdeep Kaur, Sangeeta Mahala and Sasikumar Elumalai","doi":"10.1039/D4RE00076E","DOIUrl":"10.1039/D4RE00076E","url":null,"abstract":"<p > <small>D</small>-Talose, classified as a rare and expensive sugar molecule, is gaining attraction due to its antimicrobial and anti-inflammatory properties. Its production is widely investigated by adopting biological enzymes, which is costly. However, alternative chemical methodologies have reported its formation as a side product and in minor amounts. We report for the first time its significant synthesis using <small>D</small>-galactose (which comprises whey and hemicellulose) by employing a finely tuned molybdenum oxide (MoO<small>₃</small>) solid acid catalyst. The nitric acid treatment of MoO<small>₃</small> modulated the valency ratio in Mo species (Mo<small>^5+/6+</small>), resulting in an improved Lewis acidity with up to 199 μmol g<small>⁻¹</small> acidic sites and porosity of up to 48% relative to the pristine MoO<small>₃</small>, attributed to the generated oxygen vacancies. Combined together these have assisted in an augmented <small>D</small>-talose synthesis with as high as 25% yield, 70% selectivity and 98% carbon balance in a water medium under modest reaction conditions (120 °C and 30 min). As proposed, Mo's interaction with <small>D</small>-galactose to form a Mo–sugar complex has influenced the C1–C2 carbon shift to yield <small>D</small>-talose. Furthermore, the typical isotopic labelling NMR characterization has confirmed the Bílik mechanism of C2-galactose epimerization. Overall, the heterogeneous catalytic setup represents a sustainable and feasible method for producing rare sugar for food additive and pharma applications.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2293-2305"},"PeriodicalIF":3.4,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141195341","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":"Modulation of support properties in flower-like Pt/Al2O3 nanosheet catalysts for dehydrogenation of cycloalkanes†","authors":"Mengmeng Zhu, Gang Hou, Chaoran He, Sibao Liu and Guozhu Liu","doi":"10.1039/D4RE00197D","DOIUrl":"10.1039/D4RE00197D","url":null,"abstract":"<p >Dehydrogenation of cycloalkanes derived from plastic waste presents an attractive approach for hydrogen production and plastic waste valorization. In this study, we developed Pt/Al<small>₂</small>O<small>₃</small> nanosheet catalysts with tailored support properties by adjusting the calcination temperature. Comprehensive characterization of the catalysts revealed that the support properties, including crystal phase, surface area, acid sites, hydroxyl groups, and defect sites, were modulated by increasing the heat treatment temperature. Consequently, these variations led to differences in Pt particle size, dispersion, and the chemical environment of active sites on the resulting Pt/Al<small>₂</small>O<small>₃</small> catalysts. The catalytic dehydrogenation of methylcyclohexane exhibited a volcano-like trend in terms of catalytic activities, while the stability of the catalyst showed a concave relationship with increasing calcination temperature. The Pt/Al<small>₂</small>O<small>₃</small>-700 nanosheet catalyst, prepared using a support calcined at 700 °C, exhibited exceptional catalytic activity and stability. It achieved a remarkable hydrogen production rate of 3402 mmol g<small>_Pt</small><small>⁻¹</small> min<small>⁻¹</small> at 350 °C, surpassing most Pt-based catalysts reported in the literature. In addition, this catalyst is also effective for the dehydrogenation of plastic waste derived 1,4-dimethylcyclohexane and 1,3-dimethylcyclohexane. The catalytic activity is strongly influenced by factors such as surface area, Pt particle size, the fraction of surface Pt<small>⁰</small> species, and the electronic density of surface Pt species. On the other hand, the stability of this catalyst is closely associated with acid sites and hydroxyl groups present on the Al<small>₂</small>O<small>₃</small> support. The superior performance observed in the Pt/Al<small>₂</small>O<small>₃</small>-700 catalyst can be attributed to its optimal combination of factors including a high surface area, an appropriate particle size of 1.4 nm, a desirable amount of metallic Pt species on the surface, and a moderate electron density of surface Pt species that provide a balance between accessible active sites and toluene desorption. Furthermore, its excellent stability can be attributed to an optimal ratio between acid sites and hydroxyl groups that effectively inhibit coke formation and sintering of Pt nanoparticles. This study emphasizes the importance of regulating a rational support with optimal properties to enhance the catalytic efficiency for cycloalkane dehydrogenation.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2367-2379"},"PeriodicalIF":3.4,"publicationDate":"2024-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141165508","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":"Open-source 3D printed reactors for reproducible batch and continuous-flow photon-induced chemistry: design and characterization†‡","authors":"Tom M. Masson, Stefan D. A. Zondag, Jasper H. A. Schuurmans and Timothy Noël","doi":"10.1039/D4RE00081A","DOIUrl":"10.1039/D4RE00081A","url":null,"abstract":"<p >In both batch and continuous-flow reactor technology, reproducibility can be challenging for photochemical processes due to setup variability. One major contributor to this issue is the lack of standardized reactor solutions, particularly in academic laboratories where cost is often a prohibitive factor to purchase commercially-available reactor technology. However, advancements in 3D printing technologies and the availability of high-intensity light sources present an opportunity to develop cost-effective laboratory equipment. In this work, we present a diverse set of open-source reactor designs aimed at democratizing photochemistry while reducing the barrier of expensive technology. We introduce three new reactor designs: the UFO reactor for batch reactions, the Uflow reactor for seamless transition to flow processes, and the Fidget reactor for scale-up. After detailing the design principles and rationale behind these configurations, we characterize and evaluate their performance through simulations and experiments. These designs offer a standardized and affordable point of entry for researchers interested in exploring batch and flow photochemistry.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 2218-2225"},"PeriodicalIF":3.4,"publicationDate":"2024-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00081a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141151778","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}