Reaction Chemistry & Engineering最新文献

{"title":"Pr-doped oxygen-vacancy-induced porous NiMoO4 cathode and MoS2-modified CNT anode for constructing ultra-high-performance supercapacitors","authors":"Haoran Li, Tenghao Ma, Tingting Hao, Jian Hao, Jing Wang, Yabin Wang, Zheng Zhao and Chenyu Lei","doi":"10.1039/D4RE00577E","DOIUrl":"https://doi.org/10.1039/D4RE00577E","url":null,"abstract":"<p >In this study, the sol–gel method was used to prepare NiMoO<small>₄</small> electrode materials doped with different concentrations of the rare earth element Pr. The microstructure and phase structure of the samples were thoroughly studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The results showed that the prepared materials were porous nanospheres. Due to their porous spherical shape, these structures showed a large specific surface area, providing more surface area for charge storage and release, which helped in increasing the reaction rate of the electrode, thereby improving the energy storage performance of the capacitor. Since the ionic radius of Pr differed from that of the original metal in NiMoO<small>₄</small>, the size mismatch could result in the removal of oxygen atoms from the crystal lattice, forming oxygen vacancies. The electronic structure of the material was changed, and the number of active sites increased, which affected the electrochemical properties of the material. The electrochemical performance of the rare earth Pr-doped NiMoO<small>₄</small> electrode material (Pr–NiMoO<small>₄</small>) was further tested. The experimental results showed that the Pr–NiMoO<small>₄</small> electrode exhibited excellent electrochemical performance with 0.7% Pr doping, achieving a specific capacity of 2078 F g<small>⁻¹</small> at a current density of 1 Å g<small>⁻¹</small>. Even at a current density of 5 Å g<small>⁻¹</small> and 10 000 charge and discharge cycles, the material retained 98.8% of its capacitance, showing better electrochemical stability than undoped NiMoO<small>₄</small>. An asymmetric supercapacitor was constructed using 0.7% Pr–NiMoO<small>₄</small> material (Pr–NiMoO<small>₄</small>) as the positive electrode material and MoS<small>₂</small>@C as the negative electrode material, showing a high energy density of 73.5 W h kg<small>⁻¹</small>. After 10 000 charge and discharge cycles, the capacitance retention rate of the capacitor could still be maintained at 91.9%. This study successfully proposes an effective strategy for the preparation of rare earth-doped bimetallic oxide electrode materials.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1007-1020"},"PeriodicalIF":3.4,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888481","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":"Highly efficient cobalt-modified hopcalite catalysts prepared through crednerite–spinel transformation†","authors":"D. A. Svintsitskiy, E. S. Kvasova, T. Yu. Kardash, N. A. Sokovikov, O. A. Stonkus and A. I. Boronin","doi":"10.1039/D4RE00552J","DOIUrl":"https://doi.org/10.1039/D4RE00552J","url":null,"abstract":"<p >The work presents a study and comparison of the catalytic properties of hopcalite catalysts composed of copper–manganese and copper–cobalt–manganese spinel particles in the low-temperature CO oxidation reaction. The cubic spinel structure was formed immediately under reaction conditions through the transformation of hydrothermally prepared crednerite CuMn(Co)O<small>₂</small> particles. Both the initial crednerite-type and the resultant spinel-type particles (Cu, Mn, Co)<small>₃</small>O<small>₄</small> exhibited a lamellar morphology and a uniform distribution of elements throughout their bulk and surface. It was found that the modification of the copper–manganese oxide with cobalt resulted in increased particle dispersion and a significant distortion of the crednerite crystal lattice. As a result, this modification reduced the temperature required for the crednerite-to-spinel transformation to 250 °C, whereas the unmodified catalyst is transformed after heating to 350–400 °C only. Furthermore, it was demonstrated that during the CO oxidation at room temperature, the modified spinel particles (Cu, Mn, Co)<small>₃</small>O<small>₄</small> exhibited a specific catalytic activity ∼3.5 times greater than that of the copper–manganese system. This enhancement is associated with the stabilization of a more oxidized surface state for the modified spinel particles, which may involve an increased contribution of Co<small>³⁺</small> and Mn<small>⁴⁺</small> surface species, as well as an enhancement in the overall lattice oxygen mobility.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1021-1037"},"PeriodicalIF":3.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888482","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":"Depolymerization of polydimethylsiloxanes in ammonia – a new approach to silicone recycling†","authors":"E. O. Minyaylo, A. I. Kudryavtseva, M. N. Temnikov, A. S. Peregudov, A. A. Anisimov and A. M. Muzafarov","doi":"10.1039/D4RE00566J","DOIUrl":"https://doi.org/10.1039/D4RE00566J","url":null,"abstract":"<p >This work presents a new approach to recycling silicone waste: depolymerization in ammonia. The optimal depolymerization conditions (150 °C, 0.25 mL H<small>₂</small>O, 24 h) to achieve complete polymer conversion were developed using a model siloxane fluid PMS-200. The method performance was demonstrated on model unfilled silicone rubbers obtained by classical methods of curing silicone elastomers such as hydrosilylation, condensation of functional groups and radical polymerization in the presence of benzoyl peroxide. The versatility of this approach for recycling both linear silicones (fluids and gums) and filled rubbers (fillers of different nature) was demonstrated. The completeness of the depolymerization and the analysis of the low molecular weight products were tested by SEC, GC and <small>²⁹</small>Si NMR spectroscopy. The scalability of the process has been demonstrated.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 922-930"},"PeriodicalIF":3.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698412","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":"Revelation of the photoexcitation mechanism of COF-DFB materials based on first principles","authors":"Huanjun Su, Yumeng Zhang, Weili Shi, Haoyang Shi, Yani Liu and Ying Lin","doi":"10.1039/D4RE00492B","DOIUrl":"https://doi.org/10.1039/D4RE00492B","url":null,"abstract":"<p >A two-dimensional covalent organic framework (COF) material successfully prepared in the experiment exhibits good light absorption performance, but its internal mechanism is still unclear. A deep understanding of the excitation mechanism of COF materials is of great significance for the preparation and modification of two-dimensional materials. First, the geometric structure of COF-DFB was determined using first-principles and quantum chemical methods, revealing a pore size of 11.62 Å. Secondly, the electron–hole distribution of each excited state of COF-DFB with an oscillator strength greater than 0.1 was further analyzed. It was found that in most excited states of COF-DFB, the electrons are mainly distributed on the TMBP monomer, while the holes are concentrated between TMBP (2,2′,6,6′-tetramethyl-4,4′-bipyridine) and DFB (1,4-diformylbenzene). Finally, the UV-visible spectrum of COF-DFB shows that its maximum absorption wavelength is 413.8 nm. These results indicate that COF-DFB possesses excellent photoelectric properties and demonstrates significant application potential in the field of photocatalysis.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 999-1006"},"PeriodicalIF":3.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888496","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":"Energetical analysis of a method for the scale-up of a microwave flow P-esterification by recirculation†","authors":"József Schindler, István Greiner and György Keglevich","doi":"10.1039/D4RE00622D","DOIUrl":"https://doi.org/10.1039/D4RE00622D","url":null,"abstract":"<p >In a previous communication, we described a flow chemical microwave implementation, where the reaction mixture is circulated. In this way, the given reactor capacity can be increased by up to ten times without any special modifications. It was investigated how the flow rate affects the required number of cycles, and hence the time required to achieve the maximum conversion. The role of the ionic liquid catalyst, and the effect of the increase in the volume on the outcomes were also studied. In this paper, we analyse further the data obtained from an energetic point of view. It was observed that the power of the magnetron of the microwave reactor is consumed by the sets marked by higher flow rates and by increased volumes. The direct esterification of phenyl-<em>H</em>-phosphinic acid with butyl alcohol, which has been previously reported under microwave conditions, was chosen as a model reaction.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 856-863"},"PeriodicalIF":3.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698405","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":"Immobilized laccase of Galactomyces geotrichum on modified bentonite and its use in the bioremediation of olive mill wastewater†","authors":"Khadijeh Pourkhanali and Gholam Khayati","doi":"10.1039/D4RE00470A","DOIUrl":"https://doi.org/10.1039/D4RE00470A","url":null,"abstract":"<p >This work investigates the immobilization of laccase obtained from <em>Galactomyces geotrichum</em> onto modified bentonites. The structures of the composites were examined using SEM, FTIR, and BET techniques. Biocatalysts were evaluated in terms of activity, stability and kinetic parameters. Among the immobilized laccases, GDU-bent-lac exhibited the highest efficacy in operational (96% after 10 cycles), thermal (61% within 24 h at 65 °C), and storage (79.69% for 30 days) stabilities. Results suggested that the Langmuir model better correlated with the obtained data than the Freundlich isotherm. Results of the biodegradability study indicated that the increase in the biodegradability index of olive mill wastewater was remarkable when CTAB-bent-lac was used. Additionally, the bulk increase in the biodegradability was related to the support before laccase immobilization (0.43), and moreover, immobilization enhanced the biodegradability to some extent (0.46). In this research, a strong laccase-producing microorganism that was isolated from olive mill wastewater was used for the bioremediation of the same wastewater. To the best of our knowledge, the immobilization of laccase produced by <em>G. geotrichum</em>, isolated from OMW, onto modified bentonites has not been published earlier. Furthermore, the feasibility of using immobilized laccase to increase the biodegradability of OMW was investigated for the first time.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 825-838"},"PeriodicalIF":3.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698429","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":"Identifying the ideal thermodynamics of non-stoichiometric oxygen-carrier materials for chemical looping water-gas shift†","authors":"M. Selim Ungut, Ian S. Metcalfe and Wenting Hu","doi":"10.1039/D4RE00454J","DOIUrl":"https://doi.org/10.1039/D4RE00454J","url":null,"abstract":"<p >With the growth in importance of H<small>₂</small> both industrially and as a potential energy vector along the pathway to achieving future environmental sustainability, there is an increasing need for cleaner and more efficient methods of H<small>₂</small> production. One promising short-term solution is to perform the water-gas shift reaction for H<small>₂</small> production in a chemical looping reactor to produce separate H<small>₂</small> and CO<small>₂</small> streams, thereby reducing equipment size and the cost of downstream CO<small>₂</small> separation. Non-stoichiometric perovskite oxides have been identified as promising oxygen carrier materials (OCMs) for the chemical looping water-gas shift (CLWGS) process as they can be engineered to allow rapid oxygen uptake kinetics, and also benefit from a thermodynamic advantage allowing higher conversions than that of conventional mixed feed reactor systems at the same temperature. The relationship between the oxygen non-stoichiometry of the solid OCM and the equilibrium oxygen partial pressure of the gas phase streams plays an important role in determining the gas conversions and usable oxygen capacity of the OCM. In this work, an optimal relationship between the two material properties in a thermodynamically limited system is proposed, and an equilibrium packed-bed reactor model is used for validation. The effect on conversions was investigated by varying the thermodynamics of the non-stoichiometric material relative to the proposed optimal case. More generally, an analogue of the pinch analysis can be used to analyse chemical looping water-gas shift reactions and similar processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 800-809"},"PeriodicalIF":3.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00454j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698427","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":"Crystal facet engineering of metal oxides for upgrading biomass-derived oxygenates: a perspective","authors":"Zihao Liu, Yonghua Guo, Qingfeng Ge and Xinli Zhu","doi":"10.1039/D4RE00562G","DOIUrl":"https://doi.org/10.1039/D4RE00562G","url":null,"abstract":"<p >Coordinatively unsaturated metal cations and oxygen anions on the surface of amphoteric metal oxides serve as acid and base centers, respectively, enabling a number of acid/base-catalyzed reactions. In particular, the O atom of oxygenates can readily coordinate with surface metal cations and can therefore initiate various reactions that are important for upgrading biomass-derived oxygenates. Metal oxide catalysts prepared <em>via</em> conventional methods expose various facets with distinct properties, making it difficult to elucidate the reaction chemistry and mechanism mediated on metal oxides at an atomic level. Advances in synthesis of nanocrystals of metal oxides with predominantly exposing a certain facet allow one to explore the reaction chemistry on well-defined metal oxide facets under real reaction conditions and thus may provide a powerful approach to investigate the facet-dependent structure–activity relationships of metal oxide-mediated reactions. In this perspective, we first elaborated on the fine structure and properties of various facets of TiO<small>₂</small> and CeO<small>₂</small> and then surveyed the dehydration/dehydrogenation of alcohols, ketonization of carboxylic acids, and aldol condensation of ketones and aldehydes mediated by metal oxides. In particular, we discussed the relationship between catalytic performances and the facet-dependent acid–base property and fine surface geometrical structure. Finally, we described challenges and opportunities associated with future research on metal oxide-mediated reactions <em>via</em> crystal facet engineering.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 750-767"},"PeriodicalIF":3.4,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698422","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":"Selenium-modified microgels as interfacial catalysts for the heterophase oxidation of aromatic aldehydes†","authors":"Anastasiia Pavliuk, Oliver Fiukowski, Jan Wagner, Tetiana Kharandiuk, Volodymyr Ivasiv, Roman Nebesnyi, Uwe Schnakenberg and Andrij Pich","doi":"10.1039/D4RE00516C","DOIUrl":"https://doi.org/10.1039/D4RE00516C","url":null,"abstract":"<p >The use of selenium-modified microgels as interfacial catalysts offers a promising solution for the efficient and environmentally friendly oxidation of aromatic aldehydes. Our study highlights the use of mild reaction conditions (30–50 °C) and hydrogen peroxide as a green oxidant, taking advantage of a heterophase reaction system for the ease of product separation. The effectiveness of this system is demonstrated by the high yield of benzoic acid (95.6% with a selectivity of 96.6%) achieved in a toluene/water system at 50 °C and 8 hours reaction time. The versatility of this catalytic system is further highlighted by its successful application to various aldehydes – anisaldehyde (28.5% yield of anisic acid and 35.2% yield of mequinol), cinnamaldehyde (29.8% yield of cinnamic acid and 9.8% yield of hydrocoumarin), and veratraldehyde (39.0% yield of 3,4-dimethoxyphenol). Notably, the selenium-modified microgels exhibit excellent surfactant properties and interfacial catalytic activity in diverse heterophase organic/water solvent systems, such as chloroform/water (70.9% yield of benzoic acid), ethyl acetate/water (53.6% yield of benzoic acid), and 1-octanol/water (25.5% yield of benzoic acid and 23.3% yield of octylbenzoate). This adaptability expands the potential applications of these microgel catalysts. Moreover, the ease of catalyst recovery and good reusability of the microgel catalysts were confirmed over multiple reaction cycles, making them an attractive alternative for sustainable synthesis of aromatic acids and other oxidation processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 782-789"},"PeriodicalIF":3.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698425","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 synthesis of uniform silicalite-1 zeolite via a micro-liquid film reactor-assisted approach†","authors":"Jindong Ji, Hetong Wang, Guoli Fan, Minghao Zhao and Feng Li","doi":"10.1039/D4RE00556B","DOIUrl":"https://doi.org/10.1039/D4RE00556B","url":null,"abstract":"<p >In this work, silicalite-1 (S-1) zeolites with a uniform size of about 200 nm were rapidly synthesized by utilizing a micro-liquid film (MLF) reactor assisted hydrothermal method in a short period of 2 h, where the synthesis mixture solution underwent high-speed rotation and shear treatment in a thin liquid film zone within a short mixing time of 1–10 min at the premixing stage, yielding a homogeneous zeolite precursor colloidal suspension. It was revealed that the MLF reactor significantly enhanced the blending of the aqueous and organic phases containing the structure-directing agent and the silicon source, and the resulting homogeneous microenvironment of the zeolite precursor colloidal suspension facilitated the following hydrolysis process of the silicon source and polycondensation of initial structural units ([SiO<small>₄</small>]) to a large extent, thereby greatly accelerating nucleation and crystallization processes and thus yielding uniform S-1 zeolite crystals. The present findings provide a viable, economical, and scalable strategy for rapid synthesis of various zeolite materials applied in advanced heterogeneous catalytic reactions.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 864-875"},"PeriodicalIF":3.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698406","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}