Reaction Chemistry & Engineering最新文献

{"title":"Linear scaling relationships in homogeneous photoredox catalysis†","authors":"Kareesa J. Kron and Shaama Mallikarjun Sharada","doi":"10.1039/D4RE00419A","DOIUrl":"https://doi.org/10.1039/D4RE00419A","url":null,"abstract":"<p >This work investigates two competing pathways for the terphenyl radical anion in the photoredox catalytic cycle for CO<small>₂</small> reduction – the desired electron transfer to CO<small>₂</small> and the undesired carboxylation and deactivation of the terphenyl catalyst. A linear relationship is identified between the energetics of the two pathways when trends are examined <em>via p</em>-substitutions to the three isomeric forms of terphenyl. Analogous to linear scaling relationships in heterogeneous catalysis and electrocatalysis, this correlation highlights intrinsic bounds on catalyst performance towards photoredox CO<small>₂</small> reduction.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3105-3109"},"PeriodicalIF":3.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672265","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":"Immobilization of cationic dye on photoluminescent hydroxyapatite particles through a citric acid bonding layer†","authors":"Daichi Noda, Wanyu Shi, Aiga Yamada, Zizhen Liu and Motohiro Tagaya","doi":"10.1039/D4RE00277F","DOIUrl":"https://doi.org/10.1039/D4RE00277F","url":null,"abstract":"<p >We demonstrated the surface functionalization using citric acid (Cit) as a bonding layer on hydroxyapatite (HAp) nanoparticles. The bonding layer on the Eu(<small>III</small>) ion-doped HAp nanoparticles could be immobilized with the larger amount of cationic porphyrin. The interactions between the immobilized molecules were enhanced at the monomer state with increasing the amount.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2863-2867"},"PeriodicalIF":3.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142518298","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":"ChemPren: a new and economical technology for conversion of waste plastics to light olefins","authors":"Anne Gaffney, Debtanu Maiti, Debasish Kuila and Gennaro Mafia","doi":"10.1039/D4RE00354C","DOIUrl":"https://doi.org/10.1039/D4RE00354C","url":null,"abstract":"<p >With the ever-increasing demand for plastics, sustainable recycling methods are key necessities. The current plastics industry can manage to recycle only 10% of the 400 million metric tons of plastic produced globally. Waste plastics, in the current infrastructure, land up mostly in landfills. Although a lot of research efforts have been spent on processing and recycling co-mingled mixed plastics, energy-efficient sustainable and scalable routes for plastic upcycling are still lacking. Catalytic valorization of waste plastic feedstock is one of the potential scalable routes for plastic upcycling. Silica-alumina based materials, and zeolites have shown a lot of promise. A major interest lies in restricting catalyst deactivation, and refining product selectivity and yield for such catalytic processes. This article highlights ChemPren technology as a clean energy solution to waste plastic recycling. Co-mingled, mixed plastic feedstock along with spray dried, attrition resistant, ZSM-5 containing catalysts is preprocessed with an extruder to form optimally sized particles and fed into a fluidized bed reactor for short contact times to produce selectively and in high yields ethylenes, propylenes and butylenes. This techno-economic perspective indicates that the ChemPren technology can produce propylene at $0.16 per lb, whereas the current selling price of virgin propylene is $0.54 per lb. This technology can serve as a platform for mixed plastic upcycling, with more advancements necessary in the form of robust and resilient catalysts and reactor operation strategies for tuning product selectivity.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3100-3104"},"PeriodicalIF":3.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672264","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":"One-pot enzymatic synthesis of l-5-methyltetrahydrofolate from folic acid using enzyme cascades†","authors":"Linjiang Zhu, Yuxin Wang, Linyan Pan, Enyong Lin, Jiayan Wang and Xiaolong Chen","doi":"10.1039/D4RE00237G","DOIUrl":"https://doi.org/10.1039/D4RE00237G","url":null,"abstract":"<p > <small>L</small>-5-Methyltetrahydrofolate (<small>L</small>-5-MTHF) is an active form of folate and widely used as a nutraceutical due to its high bioavailability. Herein, we report an efficient one-pot three-enzyme cascade reaction for the production of <small>L</small>-5-MTHF starting from synthetic folic acid (FA). The newly-designed synthesis route was validated by enzyme screening and process optimization. The highly-active dihydrofolate reductase from <em>Lactobacillus bulgaricus</em> (<em>Lbu</em>DHFR) was identified for asymmetric hydrogenation towards unnatural substrate FA, which could remarkably increase the synthetic efficiency. Dimethylsulfoniopropionate-dependent demethylase (DmdA) was successfully employed for directly converting tetrahydrofolate into <small>L</small>-5-MTHF using a cheap methyl donor. <em>Rco</em>DmdA from marine bacteria <em>Ruegeria conchae</em> was selected due to its high tolerance against the inhibition of the demethylated by-product. The optimal one-pot enzymatic synthesis could completely convert 34 mM of FA into 32.5 mM of <small>L</small>-5-MTHF with a molar conversion rate of 95.6%. No FA, dihydrofolate or tetrahydrofolate were detected in the final reaction mixture. Therefore, the new one-pot enzymatic method, circumventing the need for a transition metal catalyst, an unstable strong reductant and crystallization resolution, is proved to be simple, cost-effective, and easy to scale up for the green synthesis of <small>L</small>-5-MTHF.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3110-3115"},"PeriodicalIF":3.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672266","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":"Mixed-conducting ceramic membrane reactors for hydrogen production","authors":"Jingjing Tong, Peng Zhang, Fuwei Zhuang, Yanyan Zheng, Binyan Liu, Xiangping Qiao and Xuefeng Zhu","doi":"10.1039/D4RE00372A","DOIUrl":"https://doi.org/10.1039/D4RE00372A","url":null,"abstract":"<p >Hydrogen is widely used in industrial chemistry and acts as a promising clean energy carrier that can be produced from different hydrocarbons and water. Currently, the main sources of hydrogen are fossil fuels; however, they are associated with large CO<small>₂</small> emissions. Alternatively, green hydrogen produced from water electrolysis using renewable energy is still far from large-scale industrial application owing to the poor reliability of renewable energy and water electrolysis. Therefore, the production of blue hydrogen, coupled with the CO<small>₂</small> capture process, will play a dominant role in the near future in commercial hydrogen production. In this review, membrane reactor technologies based on ceramic-based dense membranes are comprehensively introduced. Membrane reactors are classified into three types according to the properties of the conductive carrier of membrane materials: (1) mixed protonic and electronic conductor (MPEC) membrane reactors, (2) mixed oxide-ionic and electronic conductor (MOEC) membrane reactors, and (3) mixed oxide-ionic and carbonate-ionic conductor (MOCC) membrane reactors. Their working principle, membrane materials, hydrogen sources, operating conditions, and performance are summarized. Finally, the challenges and prospectives of these membrane reactors are discussed for their future development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3072-3099"},"PeriodicalIF":3.4,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00372a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672263","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":"Syngas production from phenolic pollutants via a series of hydroxylation, ring cleavage, and aqueous-phase reforming catalyzed by a hydrotalcite-supported Fe–Mn–Ni alloy†","authors":"Hanifrahmawan Sudibyo, Daniela V. Cabrera, Rodrigo Labatut, Calvin J. Supriyanto, Budhijanto Budhijanto and Adhika Widyaparaga","doi":"10.1039/D4RE00348A","DOIUrl":"https://doi.org/10.1039/D4RE00348A","url":null,"abstract":"<p >A trifunctional catalyst facilitating a series of hydroxylation, oxidative ring opening, and aqueous-phase reforming reactions was developed to convert phenolic wastewater into syngas. The definitive screening design experiment at 250 °C for 5 h with 1.75% H<small>₂</small>O<small>₂</small> and 2 wt% catalyst loading demonstrated the importance of Fe, Mn, and Ni among the first-row transition metals to be impregnated into hydrotalcite to acquire the trifunctional feature. The surface chemistry characterization revealed that they improved the amount of strong and weak Brønsted (SBrA and WBrA) and Lewis (SLA and WLA) acidic active sites. The mechanistic roles of these sites <em>via</em> semi-continuous kinetic investigation at 200–300 °C for 1–5 h with 1.75% H<small>₂</small>O<small>₂</small> and 2 wt% catalyst loading were unraveled: (1) SBrA (surface metal oxyhydroxides) facilitated hydroxylation and homolytic cleavage producing hydroxyphenols; (2) WBrA (surface metal hydroxides) promoted ring opening of hydroxyphenols yielding oxo- and di-carboxylic acids; (3) WLA (mineral phase with a tetrahedral coordination) catalyzed reforming of acids into syngas; and (4) SLA (mineral phase with an octahedral coordination) improved the H<small>₂</small> yield by promoting the water–gas shift reaction. The optimal content of Fe, Mn, and Ni was 49.4, 21.2, and 29.4 wt%, respectively, from 20 wt% of active metals on the support to achieve the maximal organic carbon removal (∼82%) and H<small>₂</small> yield (∼80%) with a CO-to-H<small>₂</small> ratio of 0.6, useful for chemical building block synthesis. The optimized catalyst demonstrated high activity and reusability, with a turnover number and frequency of ∼1 × 10<small>⁶</small> and ∼6 × 10<small>⁴</small> s<small>⁻¹</small>, respectively, marking a breakthrough in sustainable syngas production.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3285-3298"},"PeriodicalIF":3.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672284","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 production of para-xylene from biomass-derived 2,5-dimethylfuran through tandem Diels–Alder/dehydration reactions with a bifunctional Ga,Al-zeolite catalyst†","authors":"Jaeyul Kim, Sungmin Han and Jeffrey D. Rimer","doi":"10.1039/D4RE00362D","DOIUrl":"https://doi.org/10.1039/D4RE00362D","url":null,"abstract":"<p >Here we demonstrate that Ga,Al-*BEA zeolites are effective bifunctional catalysts for <em>para</em>-xylene (<em>p</em>-xylene) production from bio-derived 2,5-dimethylfuran (DMF) through tandem Diels–Alder/dehydration reactions. A series of catalysts was synthesized <em>via</em> direct (one-pot) and post-synthesis techniques to introduce Brønsted and Lewis acid sites. The synthesis approach employed in this study avoids cost- and time-intensive processes typically associated with the preparation of metal-substituted *BEA zeolite catalysts for <em>p</em>-xylene production. Our findings reveal that Ga,Al-*BEA catalysts enhance DMF conversion and <em>p</em>-xylene selectivity in comparison to Al-*BEA zeolite. The pairing of Ga and Al in a single catalyst yields fewer byproducts, such as 2,5-hexanedione, 1-methyl-4-propyl-benzene, alkylated products, and oligomers. Comparisons of zeolites prepared with different Ga content reveal a higher turnover frequency for DMF conversion to <em>p</em>-xylene over Ga,Al-*BEA catalysts prepared by a one-pot synthesis compared to Al-*BEA catalysts. We observed a correlation between Ga content and <em>p</em>-xylene selectivity and yield, which is attributed to the Brønsted acidity of Ga framework sites (with reduced acid strength compared to Al sites) and to the Lewis acidity of extra-framework Ga species. The latter contribution was confirmed by analysis of Ga-impregnated Al-*BEA zeolites, which are less active than framework species but have a positive effect on <em>p</em>-xylene selectivity. Our collective findings indicate that tuning zeolite acidity by optimizing the amount of heteroatom incorporation in the crystal framework to tailor the speciation and strength of acid sites is beneficial to maximize <em>p</em>-xylene production from renewable resources.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3277-3284"},"PeriodicalIF":3.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142672283","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":"Application of the three-reactor hydrogenation process in the recycling utilization of waste lubricating oil and study on the catalyst deactivation mechanism","authors":"You Fang, Peng Zhang, Mengya Guo, Shuke Guo, Fujiang Wang and Mingxing Tang","doi":"10.1039/D4RE00323C","DOIUrl":"10.1039/D4RE00323C","url":null,"abstract":"<p >In the recycling of waste lubricating oil, the rapid deactivation of catalysts during the hydrotreating process limits their industrial application. In this paper, a three-reactor process is proposed for the refining of waste lubricating oil, which is compared with the conventional two-reactor process. Experimental results reveal that the three-reactor technique demonstrates enhanced performance in hydrodesulfurization (HDS), hydrodechlorination (HDCl), hydrodenitrogenation (HDN), hydro-decolorization, and demetallization, effectively doubling the service life of the catalysts. Characterization of the deactivated catalysts identifies carbon deposition, silicon (Si) poisoning, and boron (B) poisoning as the primary factors contributing to catalyst deactivation. The presence of a protective agent (the second catalyst) within the three-reactor process effectively removes Si and B, thereby mitigating the Si and B poisoning of the primary hydrogenation catalyst, and extending the catalyst's lifespan. This approach offers a viable solution to the challenge of frequent catalyst deactivation encountered during the high-value utilization of waste lubricating oils, thereby providing an effective pathway for overcoming this issue in the chemical industry.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3257-3266"},"PeriodicalIF":3.4,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00323c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258667","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":"Flexible carbon fibres with magnetic ZIF-67 as a core layer and in situ grown NiMn-LDH nanosheets as a shell layer for microwave absorption†","authors":"Xiaofang Ma, Ying Huang, Xiaoxiao Zhao, Meng Yu, Yan Gao, Bing Gao and Sijiao Xiang","doi":"10.1039/D4RE00353E","DOIUrl":"10.1039/D4RE00353E","url":null,"abstract":"<p >Fabrication of high-performance microwave absorbers by assembling multi-dimensional nanocomponents into core–shell electromagnetic structures has been shown to be a new manufacturing strategy. In this work, a novel core–shell carbon-fibres@ZIF-67@NiMn-layered double hydroxide (NiMn-LDH) film with excellent electromagnetic wave absorption was obtained by electrospinning ZIF-67 inside carbon fibres and subsequent solvothermal process with NiMn-LDH. With the synergistic effects of Co particles in ZIF-67 increasing magnetic loss, the appropriate proportion of the carbon fibres as a carbon source improves dielectric loss and provides a carrier for NiMn-LDH. Furthermore, NiMn-LDH at the outer shell improves impendence matching. Co/carbon fibres@NiMn-LDH (Co/CF@NiMn-LDH) was composited at a thickness of 2.8 mm with minimum reflection loss (<em>R</em> of −53 dB), and it also has good flexibility. The EAB of the obtained CF@NiMn-LDH composite reaches 6.7 GHz. This work provides a reference for the application of flexible carbon matrix composites in the electromagnetic wave absorption field.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3299-3310"},"PeriodicalIF":3.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258669","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":"Utilizing 2D metal halide perovskite thin films as highly tuneable surfaces for orientation control of energetic materials†","authors":"Natalie Smith-Papin, Meagan Phister, Ashley Conley, Nathan Swami, Zbigniew Dreger and Gaurav Giri","doi":"10.1039/D4RE00206G","DOIUrl":"10.1039/D4RE00206G","url":null,"abstract":"<p >The development of high performing and stable energetic materials (EMs) is a focus for a variety of applications including explosives, propellants, and pyrotechnics. To enhance stability, energetic crystals are often interfaced with materials such as chemical binders, which can introduce a variety of physiochemical phenomena ultimately leading to unpredictable stability and performance within the composite. Therefore, a thorough understanding of how energetic crystals behave when interfaced with various chemical functionalities is crucial for designing safer, high performing energetic formulations. This work provides a fundamental insight into interactions between a high performing energetic material, CL-20 (hexanitrohexaazaisowurtzitane), and other materials' surfaces. Highly controlled, tunable 2D metal-halide perovskite (2D MHP) templates with tunable periodicity and chemistry were created and used as a template layer to influence nucleation and growth of CL-20 crystals. All MHP/CL-20 bilayer films exhibit small, nonuniform crystalline deposit morphology for the CL-20 crystals with β-CL-20 polymorphic structure. While most MHP films template the formation of β-CL-20 crystals with a (111) preferential orientation, PbPMA<small>₂</small>Cl<small>₄</small>/β-CL-20 films crystallize with a (020) preferential orientation. The results presented herein suggest interfacial energy minimization between the two bilayer components is the dominant driving force behind the CL-20 preferential orientations. This methodology can potentially be used for developing techniques for growing energetic crystals with desired morphology, packing density and crystallographic orientation.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3248-3256"},"PeriodicalIF":3.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00206g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258670","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}