Walaa A. Elhamdy , Abd El-Aziz A. Said , Mohamed N. Goda , Kamal M.S. Khalil
{"title":"Promotional effect of CeO2 and Fe2O3 species on mesoporous silica as efficient catalysts for the vapor-phase dehydration of iso-butyl alcohol to isobutylene","authors":"Walaa A. Elhamdy , Abd El-Aziz A. Said , Mohamed N. Goda , Kamal M.S. Khalil","doi":"10.1016/j.apcata.2025.120352","DOIUrl":"10.1016/j.apcata.2025.120352","url":null,"abstract":"<div><div>CeO₂–Fe₂O₃ binary oxides were effectively incorporated into mesoporous spherical silica (MCM-41) via a sol–gel technique. The resultant CFO/MCM-41 nanocomposites, with metal loadings ranging from 3 to 30 wt%, were subsequently calcined at 550 °C and assessed as catalysts for the gas-phase dehydration of isobutyl alcohol. Structural and surface analyses using XRD, TG-DTA, ATR-FTIR, BET, TEM, EDX, XPS, and pyridine-adsorbed FTIR confirmed the formation of thermally stable, well-dispersed active phases, as well as the presence of both Lewis and Brønsted acid sites. The differences in catalytic activity among these nanocomposites were closely linked to variations in their acidity. Among all the catalysts, the 10 wt% CeFeO₃/MCM-41 sample demonstrated the best performance at 350 °C, achieving approximately 92 % isobutanol conversion, 100 % selectivity toward isobutylene, and a butene production rate of 45.10 mmol g⁻¹ h⁻¹ . The catalyst also showed excellent stability across five reuse cycles. The outstanding catalytic performance and stability were directly correlated with the material's enhanced structural integrity and optimized textural properties. Furthermore, XPS analysis revealed that the Ce<sup>3 +</sup>/Ce<sup>4+</sup> and Fe<sup>2+</sup>/Fe<sup>3+</sup> redox states, modulated by Ce–Fe interactions, played a crucial role in tuning the catalyst’s acidity and catalytic performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120352"},"PeriodicalIF":4.7,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144071720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Engineering hybrid plasmonic nanomaterials for solar energy conversion: Insight into the structure-function relations","authors":"Fengxia Tong , Leitao Zhu , Xiaolei Bao , Xizhuang Liang , Zhaoke Zheng","doi":"10.1016/j.apcata.2025.120351","DOIUrl":"10.1016/j.apcata.2025.120351","url":null,"abstract":"<div><div>Plasmonic nanomaterials, endowed with the unique surface plasmon resonance (SPR) effect, offer a promising route to convert low-intensity solar energy into chemical energy with a higher efficiency. However, the significant mismatch in timescales between rapid SPR relaxation (∼100 picoseconds) and slow chemical reaction kinetics (milliseconds or seconds) poses a major obstacle to their widespread application. To overcome these challenges, it is crucial to design multicomponent plasmonic nanostructures and establish efficient charge carrier channels. This review focuses on the effect of unique structures of plasmonic nanomaterials with precise geometries on catalytic performance. The key design strategies for hybrid plasmonic nanostructures and the deep physical and chemical mechanism have been summarized to effectively promote charge carrier excitation and migration. These strategies involve the shape, size and electronic structures tailoring of plasmonic components, an atomistic control over their coupling with other plasmonic components, doped semiconductors or non-plasmonic components, single-atom doping, crystal phase engineering as well as external field coupling. Finally, we discuss the future challenges and prospects in this field. This review aims to offer valuable insights in the design of plasmonic photocatalytic materials, ultimately accelerating the development of high-performance plasmonic photocatalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120351"},"PeriodicalIF":4.7,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144068475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalytic acetalization of glycerol to solketal using mesoporous silica, Cu-FSM-16","authors":"Rupak Kumar Singh, Vijayalakshmi Gosu","doi":"10.1016/j.apcata.2025.120350","DOIUrl":"10.1016/j.apcata.2025.120350","url":null,"abstract":"<div><div>FSM-16 and copper-incorporated Cu-FSM-16 catalysts with variable copper loadings were developed through the impregnation techniques respectively. It was used by acetalization reaction for the transformation of glycerol to solketal. The surface morphology, mesoporous structure, composition, and porosity of the prepared catalysts have been characterized by the SEM-EDAX, TEM, XRD, FTIR, XPS, and BET- surface area studies. Again, the quantification of acid sites of the catalyst was obtained from the Hammidt titration method. Furthermore, the main product (solketal) was present in the solution that was analyzed by NMR results. Moreover, maximum yield (76 %) is confirmed by using parameters with catalyst amount 7 wt% of glycerol quantity, molar ratio glycerol to acetone 1:2, time taken 2.5 h, and temperature 333 K. This catalyst has been shown consistent activity and reusability up to 4 cycles. LHHW kinetic model was also developed to find out the activation energy.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"703 ","pages":"Article 120350"},"PeriodicalIF":4.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144083861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qichao Lu, Jie Li, Chen Liang, Lei Liu, Jinxiang Dong
{"title":"FeOx clusters confined in ZSM-5 as a high-performance catalyst for Fischer-Tropsch synthesis of lower hydrocarbons","authors":"Qichao Lu, Jie Li, Chen Liang, Lei Liu, Jinxiang Dong","doi":"10.1016/j.apcata.2025.120335","DOIUrl":"10.1016/j.apcata.2025.120335","url":null,"abstract":"<div><div>Under the dual pressures of oil depletion and low-carbon transition, Fischer-Tropsch synthesis (FTS) technology offers a viable option for producing high value-added lower (C<sub>2</sub>-C<sub>4</sub>) hydrocarbons from non-oil sources. However, conventional Fe-based catalysts often suffer from deactivation due to carbon deposition and sintering. Here, we report a unique Fe-ZSM-5 catalyst synthesized by doping Fe into ZSM-5, which demonstrates excellent FTS catalytic performance. During high-temperature template removal, Fe species migrated from the zeolite framework to form highly dispersed FeO<sub>x</sub> clusters (∼2 nm). Upon treatment by syngas, these FeO<sub>x</sub> clusters aggregate to form uniformly small-sized Fe<sub>5</sub>C<sub>2</sub>@C core-shell particles distributed on ZSM-5 support. The confinement effect of the inter-crystalline structure effectively prevents the sintering of Fe<sub>5</sub>C<sub>2</sub>. The smaller Fe<sub>5</sub>C<sub>2</sub> particles exhibit controlled CO dissociation, reducing the concentration of activated carbon species (C*), and the carbon shells (∼6.5 nm) limit the departure of C*, effectively suppressing carbon deposition. This unique structure enables stable catalytic activity for over 100 hours with maintained product selectivity. The Fe-ZSM-5 catalyst achieved a C<sub>2</sub>-C<sub>4</sub> hydrocarbons selectivity of 54.52 %, nearing the 56 % theoretical limit of the Anderson-Schulz-Flory (ASF) distribution. Additionally, the hydrophobic carbon shell prevents excessive oxidation of Fe<sub>5</sub>C<sub>2</sub>, reducing CO<sub>2</sub> selectivity by ∼56 % compared to conventional Fe/ZSM-5 catalysts, significantly enhancing atomic utilization efficiency and aligning with the principles of green development.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120335"},"PeriodicalIF":4.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144068448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiaxin Song , Xiaoqiang Fan , Baijun Liu , Zhen Zhao
{"title":"Support effect on the chemical properties of Mn2O3/Na2WO4/MOx catalysts in the oxidative coupling of methane","authors":"Jiaxin Song , Xiaoqiang Fan , Baijun Liu , Zhen Zhao","doi":"10.1016/j.apcata.2025.120339","DOIUrl":"10.1016/j.apcata.2025.120339","url":null,"abstract":"<div><div>The high stability and excellent performance of NaWMn based catalysts in the oxidative coupling of methane (OCM) are expected to promote their industrial application. However, the selection of supports has significant impact on the OCM performance of NaWMn-based catalysts. In this work, we found that the addition of Na<sub>2</sub>WO<sub>4</sub>/MO<sub>x</sub> to Mn<sub>2</sub>O<sub>3</sub> can change the function of the Mn<sub>2</sub>O<sub>3</sub> catalyst from methane combustion to oxidative coupling of methane, and the Mn<sub>2</sub>O<sub>3</sub>/NaWSi catalyst exhibits the highest performance. The isotope oxygen exchange and CH<sub>4</sub>-TPSR results confirm that the appropriate oxygen exchange rate is beneficial for improving the catalytic performance of OCM reaction. H<sub>2</sub>-TPR and O<sub>2</sub>-TPD results demonstrate that the Mn<sub>2</sub>O<sub>3</sub>/NaWSi catalyst has moderate redox ability and can slowly release oxygen species at lower temperatures, matching the rate of methane consumption with the rate of C<sub>2</sub> generation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120339"},"PeriodicalIF":4.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144068447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xuying Bian, Hualiang An, Xinqiang Zhao, Yanji Wang
{"title":"Size effect of Rh/γ-Al2O3 catalyst in selective hydrogenation of dimethyl toluene-2,4-dicarbamate","authors":"Xuying Bian, Hualiang An, Xinqiang Zhao, Yanji Wang","doi":"10.1016/j.apcata.2025.120336","DOIUrl":"10.1016/j.apcata.2025.120336","url":null,"abstract":"<div><div>The selective hydrogenation of dimethyl toluene-2,4-dicarbamate (TDC) to methyl cyclohexyl-2,4-dicarbamate (HTDC) is an important process for non-phosgene synthesis of methylcyclohexane-2,4-diisocyanate (HTDI). We prepared Rh/γ-Al<sub>2</sub>O<sub>3</sub> catalysts with an Rh particle size of 1.8–6.7 nm and studied size effect on TDC selective hydrogenation. The results showed that the catalytic activities of Rh/γ-Al<sub>2</sub>O<sub>3</sub> increase monotonously with increasing Rh particle size. This demonstrated that Rh/γ-Al<sub>2</sub>O<sub>3</sub> catalyst dedicates a negative size effect or an antipathetic structure sensitivity. Based on the characterization, we found that the geometric property of Rh is the main factor affecting the activity of catalyst. Combined with the proposed Rh particle model, it was inferred that the Rh (111) plays a major role in the TDC selective hydrogenation and the terrace sites are beneficial to promote the adsorption of TDC. The study on size effect can provide a guidance for the design and preparation of highly efficient Rh-based catalysts for TDC selective hydrogenation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120336"},"PeriodicalIF":4.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143942614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A 3D fishbone-like fluorinated BiVO4 as a reducing end to enhance photocatalytic activity","authors":"Zihan Yang, Yuqing Liu, Yida Wang, Xiaotong Sun, Yanzhi Zheng, Wanning Cao, Lixia Li, Liqin Wang, Hongli Zhao, Jingkai Yang","doi":"10.1016/j.apcata.2025.120337","DOIUrl":"10.1016/j.apcata.2025.120337","url":null,"abstract":"<div><div>Photo-induced conversion of reactive oxygen species (ROS) has emerged as an effective means of removing persistent organic pollutants (POPs), but its key step of directed electron transfer from the active site to the stable O<sub>2</sub> molecule still possesses considerable challenges. In this work, we synthesized a novel 3D fishbone-like fluorinated BiVO<sub>4</sub> photocatalyst and explored the photocatalytic removal of dye-like species. The optimally fluorinated BiVO<sub>4</sub> with narrower band gap has an effective detoxification effect on MB and shows a degradation performance of 1.8 times higher than that of the original. Fluoride ions doped in the lattice and adsorbed on the surface lead to a slight increase of the electron density of BiVO<sub>4</sub> to elevate the conduction band potential and accelerate free radical activation. In addition, the degradation process of MB dye by F-BiVO<sub>4</sub> has been proposed. F-BiVO<sub>4</sub> material is proved as a promising reducing end of the F-BiVO<sub>4</sub>/g-C<sub>3</sub>N<sub>4</sub> heterojunction system.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120337"},"PeriodicalIF":4.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144068474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Dehydrogenation of ethanol to acetaldehyde catalyzed by Cu nanoparticles supported on nanorod-shaped La2O2CO3","authors":"Chao Tian , Yinghong Yue , Changxi Miao , Weiming Hua , Zi Gao","doi":"10.1016/j.apcata.2025.120334","DOIUrl":"10.1016/j.apcata.2025.120334","url":null,"abstract":"<div><div>Controllably tuning the morphology of catalysts is an effective solution to enhance the catalytic performance. Herein, we have reported how the shape effect significantly improves the performance of La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>-supported Cu catalysts in ethanol dehydrogenation to acetaldehyde. Compared with La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> nanoparticles-supported Cu catalyst, La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> nanorods-supported Cu catalyst (Cu/La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>-R) considerably improves the activity and stability. The superior performance of Cu/La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>-R is attributed to its more medium basic sites and stronger interaction between Cu species and {110} surfaces of La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> nanorods. Furthermore, DRIFT studies reveal that the support and Cu species perform a synergetic mechanism, with medium basic sites involving into dissociative activation of ethanol and Cu species serving as C−H cleavage of ethoxy intermediate and H<sub>2</sub> liberation sites. The synergetic basic sites with medium strength present on the La<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> support is helpful for enhancing the intrinsic activity of supported Cu catalyst.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120334"},"PeriodicalIF":4.7,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chun Han , Le Li , Xing Tian , Zeyu Peng , Luyao Wu , Enjuan Ma , Qian Zhang , Wei Huang
{"title":"Effect of potassium on the reaction stability of CoCu catalysts for higher alcohol synthesis from syngas","authors":"Chun Han , Le Li , Xing Tian , Zeyu Peng , Luyao Wu , Enjuan Ma , Qian Zhang , Wei Huang","doi":"10.1016/j.apcata.2025.120333","DOIUrl":"10.1016/j.apcata.2025.120333","url":null,"abstract":"<div><div>Developing the stable CoCu catalysts for higher alcohol (HA) synthesis is hindered by the dynamic evolution of complex active sites. Herein, a potassium (K)-modified strategy was proposed to address these issues. The regulating effect of K on Co and Cu sites was comprehensively explored. K doping not only enhanced the metal dispersion, but also regulated the Co<sup>0</sup>/Co<sup>δ⁺</sup> ratio and provided the hydroxyl groups (OH*). The enhanced metal dispersion was ascribed to the improved electrical conductivity, strengthening the synergistic effect. The Co<sup>0</sup> proportion of Cu-rich catalysts increased, while it decreased over Co-rich catalysts. The K-induced OH* enhanced CO adsorption ability of Cu species, improving HA selectivity and restraining the aggregation of Cu species. The higher Co<sup>0</sup> proportion mitigated the impact of Co evolution. Hence, K doping Cu-rich catalysts boosted total alcohol selectivity from 9.1 % to 17.4 %, reduced methanol fraction from 61.7 % to 37.1 %, and achieved excellent stability during 100 h test.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"702 ","pages":"Article 120333"},"PeriodicalIF":4.7,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143928329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyu Yan, Yuhan Sun, Xiaoqing Xu, Jiale Xu, Rui Huang, Renjie Ji, Chunyi Li
{"title":"High-performance B2O3/SiO2-TiO2 catalyst for propane oxidation to olefins","authors":"Xiaoyu Yan, Yuhan Sun, Xiaoqing Xu, Jiale Xu, Rui Huang, Renjie Ji, Chunyi Li","doi":"10.1016/j.apcata.2025.120329","DOIUrl":"10.1016/j.apcata.2025.120329","url":null,"abstract":"<div><div>Conventional mixed metal oxide catalysts for oxidative dehydrogenation of propane (ODHP) often face challenges in balancing propane conversion and olefin selectivity. In contrast, boron-containing catalysts can achieve higher selectivity for olefins. In this study, B<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub>-TiO<sub>2</sub> catalysts were prepared via mechanical mixing and calcination, demonstrating high activity in ODHP with propylene and ethylene as primary products. At 620 °C, propane conversion reached 60.8 %, with total olefin selectivity of 70.2 %. Unlike h-BN or BO<sub>x</sub>/carrier catalysts, B<sub>2</sub>O<sub>3</sub> was directly used as both feedstock and active component, eliminating the need for an induction period. The mixed SiO<sub>2</sub>-TiO<sub>2</sub> carrier anchored boron species on the TiO<sub>2</sub> surface, reducing boron loss and enhancing stability compared to pure SiO<sub>2</sub>-supported catalysts. These results highlight the potential of B<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub>-TiO<sub>2</sub> for efficient propane oxidative dehydrogenation to olefins.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"701 ","pages":"Article 120329"},"PeriodicalIF":4.7,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143921898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}