Catalysis Today最新文献

{"title":"Tailoring the electronic properties of TiO2 monolayers for solar driven catalysis through transition metal doping","authors":"Kati Asikainen,&nbsp;Matti Alatalo,&nbsp;Marko Huttula,&nbsp;S. Assa Aravindh","doi":"10.1016/j.cattod.2024.115144","DOIUrl":"10.1016/j.cattod.2024.115144","url":null,"abstract":"<div><div>Substitutional doping with transition metals is carried out in the Lepidocrocite phase - the stable monolayer geometry of TiO₂ - using density functional theory (DFT) methods. The doping is carried out at the differently coordinated O atom cites, producing Janus monolayer geometries. Our results indicate that key fundamental properties for photocatalysis can be tuned via doping. Monolayers doped with Ag, Au, Pd and Pt are thermodynamically stable, among all considered doping possibilities, as evident from phonon band structure calculations. Electronic structure of the Janus monolayers alters significantly, compared to pristine TiO₂, owing to the emergence of mid-gap states. Reduced band gap arises from upward shift of the valence band, suggesting enhanced visible-light response. Dopant atoms also introduce excess electrons in TiO₂ monolayers, which are found to localize at a single Ti site. This induces ferromagnetism in the doped monolayers. Furthermore, charge separation between TiO₂ and noble metal dopants is observed which is a key parameter in influencing the selectivity and activity of photocatalytic materials. Compared to the pristine TiO₂ monolayer, the Janus structure can promote water adsorption, and the Janus monolayers exhibit significantly improved activity in the hydrogen evolution reaction. These findings suggest that engineering a novel Janus TiO₂-based monolayer with a noble metal layer on the other surface can offer a potential approach to improve photocatalytic performance over pristine TiO₂.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115144"},"PeriodicalIF":5.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143180475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nb2O5 based photocatalysts for efficient generation of H2 by Photoreforming of aqueous solutions of ethanol","authors":"Alberta Genco ,&nbsp;Elisa I. García-López ,&nbsp;Bartolomeo Megna ,&nbsp;Conchi Ania ,&nbsp;Giuseppe Marcì","doi":"10.1016/j.cattod.2024.115147","DOIUrl":"10.1016/j.cattod.2024.115147","url":null,"abstract":"<div><div>A series of Nb₂O₅ semiconductors and their composites with TiO₂ have been prepared following a hydrothermal treatment at varied synthetic conditions, and tested for the photoreforming of aqueous solutions of ethanol. The photo-reforming activity has been tested under UV and natural solar light irradiation, both in the absence and in the presence of Pt as co-catalyst. Our data has shown that the Nb₂O₅-TiO₂ composite prepared by a hydrothermal treatment of three days displayed the highest photocatalytic activity, with a hydrogen production of 138 mmol_H2h⁻¹g⁻¹ under UV light (apparent quantum yield of ca. 44 %) and 40 mmol_H2kJ⁻¹g⁻¹ under natural solar light (apparent quantum yield of ca. 85 % considering only the UV fraction of sunlight). The exalted photocatalytic activity of this material was attributed to the concomitance of two favorable events, namely the possible formation of a heterojunction between the two semiconductors and the optimal ratio of them in this composite.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115147"},"PeriodicalIF":5.2,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143180284","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":"Using waste to treat waste: Catalysts from spent alkaline batteries for glycolysis of PET waste","authors":"Lin Gao ,&nbsp;Zixian Jia ,&nbsp;Lijiao Qin ,&nbsp;Haocheng Sun ,&nbsp;Xinwei Zhang ,&nbsp;Baozhong Li ,&nbsp;Xuehai Wang ,&nbsp;Jiquan Liu ,&nbsp;Jinbo Bai","doi":"10.1016/j.cattod.2024.115143","DOIUrl":"10.1016/j.cattod.2024.115143","url":null,"abstract":"<div><div>The recovery of Zn/ZnO nanoparticles from spent alkaline batteries was studied. This catalyst was employed for glycolysis of polyethylene terephthalate (PET) to produce bis(2-hydroxyethyl) terephthalate (BHET). The reaction temperature, catalyst/PET ratio and reaction time were investigated. Under the optimal conditions of 190 ℃ and 2 hours, with a catalyst/PET ratio of 2 %, the PET conversion rate and BHET yield of this process were 99 % and 81 %, respectively. The experimental results show that the catalyst exhibits high catalytic activity, is easy to separate, and has good reusability. In addition, this catalyst can deal effectively with impurities and dyes present in waste PET. Finally glycolysis kinetic studies were conducted on the reaction of PET degradation, and the activation energy of 118.8 kJ·mol⁻¹ were obtained.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115143"},"PeriodicalIF":5.2,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748445","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":"Zr-doped phosphorus-containing activating carbons catalysts for the valorization of furfural into valuables products in one-pot reaction","authors":"Rocío Maderuelo-Solera ,&nbsp;Francisco José García-Mateos ,&nbsp;Gabriela Rodríguez-Carballo ,&nbsp;Cristina García-Sancho ,&nbsp;Juana María Rosas ,&nbsp;Ramón Moreno-Tost ,&nbsp;José Rodríguez-Mirasol ,&nbsp;Tomás Cordero ,&nbsp;Pedro Maireles-Torres ,&nbsp;Juan Antonio Cecilia","doi":"10.1016/j.cattod.2024.115146","DOIUrl":"10.1016/j.cattod.2024.115146","url":null,"abstract":"<div><div>Olive stones have been used to synthesize activated carbon using H₃PO₄ as activating agent under pyrolytic treatment. Then, Zr species have been incorporated by impregnation and subsequent calcination, obtaining acid catalysts with Lewis and Brønsted sites, which are involved in the one-pot reaction of furfural in value-added products. All catalysts display a high micro- and mesoporosity. The catalysts showed different behavior as a function of the temperature, obtaining full conversion after 24 hours at 110 ºC, being mainly selective towards furfuryl alcohol and i-propyl furfuryl ether. The study at higher temperature (170 ºC) reached the full conversion after only 45 minutes, being preferentially selective towards i-propyl levulinate and γ-valerolactone. The catalysts are prone to suffer deactivation processes due to the formation of humins on the surface of the catalysts, which cause a decrease of the available active sites.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115146"},"PeriodicalIF":5.2,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143179877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective hydrogenation of furfuryl alcohol to 1,2-pentanediol over Pt/Mg2AlO catalysts with different synthesis methods","authors":"Jiamin Wang ,&nbsp;Shanhui Zhu ,&nbsp;Zexiang Lv ,&nbsp;Xiangyu Jia ,&nbsp;Xiaoming Li ,&nbsp;Mei Dong ,&nbsp;Weibin Fan","doi":"10.1016/j.cattod.2024.115145","DOIUrl":"10.1016/j.cattod.2024.115145","url":null,"abstract":"<div><div>Selective cleavage of C–O bond in biomass-derived furfuryl alcohol (FFA), with complex chemical functional groups, poses a great challenge to biomass upgrading. In this work, Pt/Mg₂AlO catalysts were prepared by urea hydrolysis (Pt-HT), coprecipitation (Pt-CP) and sol-gel (Pt-SG) methods to study the interfacial property caused by support synthesis methods during selective hydrogenation of FFA to 1,2-pentanediol (1,2-PeD). The results clearly showed that 1,2-PeD yield on Pt-HT was 60.3 %, better than those on Pt-CP and Pt-SG catalysts. The superior catalytic activity of Pt-HT is ascribed to effective adsorption and split of C–O bonds, facilitated by plentiful interfacial oxygen vacancies and Pt⁰ species. Furthermore, the superior selectivity of 1,2-PeD is related to the deforming non-parallel adsorption mode of FFA rings on Pt-HT resulting from their interaction with interfacial oxygen vacancies.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115145"},"PeriodicalIF":5.2,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748447","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":"Novel preparation of polyphenylacetylene semiconductor: Potential application in supercapacitors","authors":"Katiúscia M. Nobre Borba ,&nbsp;Letícia Guerreiro da Trindade ,&nbsp;Letícia Zanchet ,&nbsp;Sibele Pergher ,&nbsp;Urbano Diaz ,&nbsp;Fernando Rey Garcia ,&nbsp;Katia Bernardo-Gusmão","doi":"10.1016/j.cattod.2024.115134","DOIUrl":"10.1016/j.cattod.2024.115134","url":null,"abstract":"<div><div>The use of MCM-41 led to the development of a silylated hybrid material (MS), which in turn played a crucial role in obtaining semiconducting polyphenylacetylene, with a conductivity of 8.13 × 10⁻⁵ S m⁻¹. MS was also responsible for reducing the polyphenylacetylene band gap from 2.13 eV to 1.83 eV. When used in a capacitor, polyphenylacetylene exhibited stability after 3000 charge/discharge cycles and a capacitance seven times higher than that of poly(o-methoxyaniline) (POMA) polymer.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115134"},"PeriodicalIF":5.2,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757804","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":"Single atom and sub-nanometer copper clusters deposited on titania for hydrogen evolution reaction: A density functional study","authors":"Dorota Rutkowska-Zbik ,&nbsp;Vidya Kaipanchery ,&nbsp;Renata Tokarz-Sobieraj","doi":"10.1016/j.cattod.2024.115142","DOIUrl":"10.1016/j.cattod.2024.115142","url":null,"abstract":"<div><div>We present a systematic theoretical study on the applicability of the hybrid Cu_n-TiO₂ systems (n = 1 – 7) for photo electrochemical hydrogen evolution reaction. The preferred binding sites for hydrogen atom are determined. The hydrogen adopts a Cu-H-Ti bridging position when bound to Cu₁-(TiO₂)₃₄ or Cu₇-(TiO₂)₃₄ or Cu-H-Cu when bound to Cu₂-(TiO₂)₃₄ or Cu₄-(TiO₂)₃₄. In Cu_n-(TiO₂)₃₄ with n = 3, 5, 6 the H atom sits in the three coordinate site, similar to that found for its favourable position while on Cu(111). The population analysis reveals that in the selected cases, n = 1, 2, 5, 7, the hydrogen binding exhibits three centre two electron bond character. In all the cases studied here the adsorbate has a hydride character. Among the studied clusters, those containing 1, 4, and 7 copper atoms exhibit moderate Gibbs free H binding energies indicating them as the best candidates for hydrogen evolution. The obtained results are compared with data available in literature for metallic copper and other materials having isolated single Cu atom sites. Considering Cu atom efficiency as well as wide availability and use of the titania as a support, these materials may be competitive for H₂ generation.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"446 ","pages":"Article 115142"},"PeriodicalIF":5.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700422","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":"Immobilization of lipase on zeolite, silica, and silica-aluminas and its use in hydrolysis, esterification, and transesterification reactions","authors":"Kelly C.N.R. Pedro ,&nbsp;Gabrielle A.R. da Silva ,&nbsp;Mônica A.P. da Silva ,&nbsp;Cristiane A. Henriques ,&nbsp;Marta A.P. Langone","doi":"10.1016/j.cattod.2024.115141","DOIUrl":"10.1016/j.cattod.2024.115141","url":null,"abstract":"<div><div>Lipases have been immobilized on various supports to catalyze hydrolysis, esterification, and transesterification reactions efficiently. Among a broad range of materials, mesoporous silica has attracted attention thanks to its distinct characteristics and advantages, being widely used for biocatalysis applications. In this work, the lipase from <em>Thermomyces lanuginosus</em> (TLL) was immobilized on six different carriers: two zeolites HZSM-5 (SAR 25 and 280), mesoporous Si-MCM-41, and silica-aluminas Siral 10, 20, and 40. TLL was efficiently immobilized in Siral 20 (99.9 %) and Siral 40 (99.9 %) using 26 mg g⁻¹ of enzyme loading. Due to its more hydrophobic nature, Siral 40 was selected as the most suitable support for TLL immobilization using 5 mmol L⁻¹ of sodium phosphate buffer solution, pH 7, and rotational stirring as the optimum condition. The effect of protein concentration on the TLL immobilization was investigated, and the results adjusted well (R² &gt; 0.99) on the Langmuir isotherm model. The Siral 40 presented a maximum adsorption capacity equal to 169 mg_protein g_support⁻¹. The heterogeneous biocatalyst (TLL-S40) was applied in biodiesel synthesis, olive oil hydrolysis, <em>p</em>-nitrophenyl-laurate hydrolysis, and ethyl oleate synthesis. The esterification reaction was successfully catalyzed by TLL-S40, leading to a conversion 2.6-fold higher than free TLL at 30 °C. The biocatalyst was reused for three operational cycles with a retention of 34 % of its initial conversion. The results show that Siral 40, a silica-alumina material, can potentially be employed in lipase immobilization for esterification reactions.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115141"},"PeriodicalIF":5.2,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702910","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":"In Situ DDR-UV-Vis and Raman spectroscopic study of titania promoting effect on silica supported tungsten catalysts for enhanced propylene metathesis","authors":"Bhagyesha S. Patil ,&nbsp;Alejandra Torres-Velasco ,&nbsp;Hashim A. Alzahrani ,&nbsp;Skylar Pratt ,&nbsp;Juan J. Bravo-Suárez","doi":"10.1016/j.cattod.2024.115138","DOIUrl":"10.1016/j.cattod.2024.115138","url":null,"abstract":"<div><div>Tungsten based catalysts supported on silica (<em>z</em>WO_X/SiO₂) and silica promoted by titania (<em>z</em>WO_X/<em>y</em>TiO_X/SiO₂) were studied for their catalytic activity towards propylene metathesis. The catalysts were prepared by a simple incipient wetness impregnation method using a large pore SiO₂ of intermediate surface area (∼50 m²/g). Catalytic activity studies carried out in a fixed-bed reactor (723 K, 101 kPa propylene) indicated that propylene conversion increased with increasing W loading in <em>z</em>WOx/SiO₂ catalysts (<em>z</em> = 0.5−6 W/nm²). It was shown that the catalytic activity of a poorly WO_X dispersed 6WO_X/SiO₂ catalyst could be enhanced and maximized by an optimum titania promotion of 2 wt% TiO₂ (∼3 Ti/nm²). In situ differential diffuse reflectance (DDR) UV-Vis spectroscopy at reaction conditions showed that TiO_X domain size increased with increases in titania loading from isolated TiO_X to TiO_X clusters to TiO₂ nanocrystals. The UV-Vis results also evidenced the existence of highly dispersed isolated WO_X species, WO_X clusters, and WO₃ nanoparticles in the 6WO_X/<em>y</em>TiO_X/SiO₂ (<em>y</em> = 0.5−6 wt% TiO₂ or ∼0.7–9 Ti/nm²) catalysts. In situ DDR-UV-Vis, Raman, and mass spectrometry during propylene metathesis, and catalyst oxidation and reduction revealed the reasons for an optimum amount of titania promoter in 6WO_X/2TiO_X/SiO₂. They were the result of a balanced interplay between two factors: (1) enhanced WOx species dispersion due to the presence of a trimeric TiO_X cluster and (2) absence of catalyst deactivation (present at high TiO₂ loadings) due to the trimeric TiO_X cluster poor reactivity towards coke formation.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115138"},"PeriodicalIF":5.2,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142724093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Performance of copper-aluminum catalysts impregnated with potassium in NO and N2O reduction by CO","authors":"Suelen Martins Stutz Gomes,&nbsp;Samara da Silva Montani,&nbsp;Luz Amparo Palacio,&nbsp;Fatima Maria Zanon Zotin","doi":"10.1016/j.cattod.2024.115140","DOIUrl":"10.1016/j.cattod.2024.115140","url":null,"abstract":"<div><div>Three-way automotive catalysts (TWC) are based on noble metals and have two significant limitations: high cost and tendency to form, at low temperatures, nitrous oxide (N₂O), which contributes to the greenhouse effect and ozone layer depletion. Thus, it is crucial to study possible substitutes for these components. In this work, catalysts prepared from copper and aluminum hydrotalcite-like materials impregnated with potassium were studied. The formation of the hydrotalcite phase and CuO phase in the catalyst was evidenced by X-ray diffraction (XRD). Temperature-programmed reduction (TPR) results showed that the alkali metal positively influences the reducibility of the catalyst, decreasing its reduction temperature. Temperature-programmed desorption (TPD) analysis revealed electronic promotion, confirming that the presence of potassium facilitates the desorption of molecular nitrogen from the surface and decreases that of N₂O. Catalytic tests showed differences in the behavior of the catalysts depending on the pretreatment performed, suggesting that the interaction between potassium and oxidized or reduced copper gives rise to different catalytic sites. The formation of oxygen vacancies in potassium-containing catalysts, identified by XPS, and the increase in the copper metal surface area contributed to explaining the better performance of these catalysts. Also, based on the catalytic tests, more selective catalysts with the addition of potassium (minimizing N₂O formation) were obtained, especially at a ratio of 0.025 K/Cu (mol/mol) and after a reducing pretreatment. This catalyst also showed 100 % N₂O conversion in the reduction by CO at temperatures close to 100 °C, confirming its excellent performance in nitrous oxide abatement.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"447 ","pages":"Article 115140"},"PeriodicalIF":5.2,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702909","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}