Catalysis Science & Technology最新文献

{"title":"Enhancing the HER rate over Pt–TiO2 nanoparticles under controlled periodic illumination: role of light modulation†","authors":"Ettore Bianco, Fabrizio Sordello, Francesco Pellegrino and Valter Maurino","doi":"10.1039/D4CY00775A","DOIUrl":"https://doi.org/10.1039/D4CY00775A","url":null,"abstract":"<p >In hydrogen production through water splitting, two reactions are involved: the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), both with efficiency issues. In previous works, our group demonstrated the possibility of enhancing H<small>₂</small> production by conducting HCOOH photocatalytic reforming on metal–TiO<small>₂</small> nanoparticles under controlled periodic illumination (CPI) rather than continuous illumination performed at the same average incident photon flux. The enhancement was observed only over specific metals, including Pt, Pd and Rh, due to their low Tafel slopes. Hydrogen adsorption and desorption energies are strongly dependent on the potential at the metal nanoparticles, and we demonstrated the ability to use CPI to induce oscillations in the potential of the catalyst. In this work, by modulating the duty cycle and the frequency of the CPI, we observed both of these playing a key role in boosting HER. Experimental evidence suggest that the relaxation of the photopotential during the dark period is the key factor for increasing the photonic efficiency of the reaction.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7205-7211"},"PeriodicalIF":4.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00775a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798142","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":"Combining computational and experimental studies to gain mechanistic insights for n-butane isomerisation with a model microporous catalyst†","authors":"Matthew E. Potter, Lucas Spiske, Philipp N. Plessow, Evangeline B. McShane, Marina Carravetta, Alice E. Oakley, Takudzwa Bere, James H. Carter, Bart D. Vandegehuchte, Kamila M. Kaźmierczak, Felix Studt and Robert Raja","doi":"10.1039/D4CY01035C","DOIUrl":"https://doi.org/10.1039/D4CY01035C","url":null,"abstract":"<p >Microporous solid acid catalysts are widely used in industrial hydrocarbon transformations in both the fuels and petrochemical industries. The specific choice of microporous framework often dictates the acidic properties of the system, such as acid site strength and concentration. In this work we have explored the influence of acid site concentration on butane isomerisation activity and the mechanistic pathway by controlling the quantity of magnesium doped into an aluminophosphate, keeping the acid site strength and framework topology constant. By combining experimental kinetic studies, and theoretical mechanistic studies, we conclude that isobutane formation, from <em>n</em>-butane, predominantly proceeds through a bimolecular pathway. Specifically, the activity of the system is strongly linked to the presence of alkenes, and herein the precise mechanistic roles of the alkenes are explored.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7140-7151"},"PeriodicalIF":4.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01035c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798124","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":"Synthesis of Co3O4 catalysts with different morphologies and their excellent catalytic performance for soot combustion†","authors":"Xinyu Zhang, Chunlei Zhang, Siyu Gao, Xinyu Chen, Siyuan Chen, Shengran Zhou, Di Yu, Lanyi Wang, Xiaoqiang Fan, Xuehua Yu and Zhen Zhao","doi":"10.1039/D4CY01115E","DOIUrl":"https://doi.org/10.1039/D4CY01115E","url":null,"abstract":"<p >Soot particles released from diesel engines have resulted in significant environmental pollution and have been widely recognized as an important factor for haze weather conditions. Soot emissions can be effectively mitigated using catalytic purification technologies, which necessitate the development of high-efficiency catalysts. Co<small>₃</small>O<small>₄</small> catalysts with flower-, rod-, urchin-, sheet-, and cube-like morphologies were prepared <em>via</em> a hydrothermal method and were analyzed using characterization methods including XRD, SEM, and H<small>₂</small>-TPR. Compared to the other synthesized catalysts, the urchin-like (Co<small>₃</small>O<small>₄</small>-U) catalyst exhibited better redox ability, stronger oxygen adsorption and activation ability, and the ability to convert NO into NO<small>₂</small>. Therefore, the Co<small>₃</small>O<small>₄</small>-U catalyst displayed the best catalytic activity for soot combustion, with <em>T</em><small>₁₀</small>, <em>T</em><small>₅₀</small>, and <em>T</em><small>₉₀</small> values of 274 °C, 327 °C, and 359 °C, respectively. Moreover, based on the characterization and catalytic performance results, the reaction mechanisms for the Co<small>₃</small>O<small>₄</small>-U catalyst were proposed. The Co<small>₃</small>O<small>₄</small>-U catalyst possesses advantages such as a simple preparation process, economic feasibility, and excellent catalytic performance.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7071-7080"},"PeriodicalIF":4.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798118","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":"Elucidation of Ce/Zr ratio effects on the physical properties and catalytic performance of CuOx/CeyZr1−yO2 catalysts†","authors":"Mohammed Sifat, Michal Luchowski, Amol Pophali, Wenhui Jiang, Yunfan Lu, Byeongseok Kim, Gihan Kwon, Kwangsuk Yoon, Jihun Kim, Kwangjin An, Sang Eun Shim, Hocheol Song and Taejin Kim","doi":"10.1039/D4CY01012D","DOIUrl":"https://doi.org/10.1039/D4CY01012D","url":null,"abstract":"<p >Although cerium oxide (CeO<small>₂</small>) is widely used as a catalyst support, its limited defect sites and surface oxygen vacancy/mobility should be improved. The incorporation of zirconium (Zr) in the cerium (Ce) lattice is shown to increase the number of oxygen vacancies and improve catalytic activity. Using a fixed surface density (SD) of copper (∼2.3 Cu atoms per nm<small>²</small>) as a surface species, the role of the support (Ce<small>_<em>y</em></small>Zr<small>_{1−<em>y</em>}</small>O<small>₂</small> (<em>y</em> = 1.0, 0.9, 0.6, 0.5, and 0.0)) and defect site effects in the CO oxidation reaction was investigated. Spectroscopic (<em>e.g.</em>, Raman, XRD, XPS) and microscopic (<em>e.g.</em>, SEM-EDX, HR-TEM) characterization techniques were applied to evaluate the defect sites, crystallite size, lattice parameters, chemical composition, oxidation states of elements and microstructure of the catalysts. The CO oxidation reaction with varied CO : O<small>₂</small> ratios (1 : 5, 1 : 1, and 1 : 0.5 (stoichiometric)) was used as a model reaction to describe the relationship between the structure and the catalytic performance of each catalyst. Based on the characterization results of Ce<small>_<em>y</em></small>Zr<small>_{1−<em>y</em>}</small>O<small>₂</small> materials, the addition of Zr causes physical and chemical changes to the overall material. The inclusion of Zr into the structure of CeO<small>₂</small> decreased the overall lattice parameter of the catalyst and increased the number of defect sites. The prepared catalysts were able to reach complete CO conversion (∼100%) at low temperature conditions (&lt;200 °C), each showing varied reaction activity. The difference in CO oxidation activity was then analyzed and related to the structure, wherein Cu loading, surface oxygen vacancies, reduction–oxidation ability, CuO<small>_<em>x</em></small>–support interaction and oxygen mobility in the catalyst were the crucial descriptors.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7107-7123"},"PeriodicalIF":4.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798121","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":"Catalytic activity and stability of NiPt/C catalysts for the synthesis of iso-butanol from methanol/ethanol mixtures†","authors":"Joachim Pasel, Johannes Häusler, Ralf Peters and Detlef Stolten","doi":"10.1039/D4CY01061B","DOIUrl":"https://doi.org/10.1039/D4CY01061B","url":null,"abstract":"<p >Mixtures of sustainably produced ethanol and methanol can serve as educts for the synthesis of higher alcohols, which are considered carbon-neutral components and feedstocks for the transportation and chemical sectors. In this respect, this study focused on bi-metallic NiPt catalysts supported on activated carbon for the synthesis of iso-butanol. Reaction temperature, time on stream, and the inlet concentration of ethanol were varied to investigate the influence of these parameters on ethanol conversion, the selectivities towards iso-butanol, and other reaction products, as well as the space–time yield of the NiPt/C catalyst. In addition, kinetic parameters were determined. It was found that a reaction temperature of 165 °C was most suitable for the selectivity towards iso-butanol. Activation energies were calculated to the range between 110 kJ mol<small>⁻¹</small> and 120 kJ mol<small>⁻¹</small>. TEM experiments revealed that there was no ageing of the catalytically active species of the Ni<small>₉₉</small>Pt<small>₁</small>/C catalyst during iso-butanol synthesis.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7048-7060"},"PeriodicalIF":4.4,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01061b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798103","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":"All-in-one Rh(iii)-covalent organic framework for sustainable and regioselective C(sp2)–H bond functionalization†","authors":"Luohe Wang, Junnan E, Xiubin Bu, Jing Zeng, Xiaobo Yang, Hua Fu and Zhen Zhao","doi":"10.1039/D4CY01098A","DOIUrl":"https://doi.org/10.1039/D4CY01098A","url":null,"abstract":"<p >Rh(<small>III</small>)-catalyzed regioselective C(sp<small>²</small>)–H bond functionalization is a facile tool for precisely synthesizing valuable organic molecules. However, challenges such as cost, reusability, and metal residue issues are always encountered in pharmaceutical applications under homogeneous reaction conditions. Herein, we report the synthesis of a Rh(<small>III</small>)-covalent organic framework (RhCOF-SYNU-1) for heterogeneous regioselective C(sp<small>²</small>)–H bond functionalization. The suitable post-modification and metal immobilization endow RhCOF-SYNU-1 with multiple characteristics, including adaptable and homo-dispersed Rh(<small>III</small>) centers, an extended conjugation system, and considerable stability. Hence, RhCOF-SYNU-1 serves as an all-in-one catalyst by integrating the roles of transition-metal catalyst, photocatalyst, and metal-center ligand. It also demonstrates excellent catalytic performance in various visible-light-driven or thermal regioselective C(sp<small>²</small>)–H bond functionalization reactions. Notably, the inherent robustness of RhCOF-SYNU-1 ensures its long-term use and simultaneous recycling with Cu oxidant under sophisticated organic reaction conditions, constituting a beneficial strategy for sustainable Rh(<small>III</small>) catalysis.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7061-7070"},"PeriodicalIF":4.4,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798104","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":"Solar-driven triple photocatalytic action of defective S-doped g-C3N4 for 1,4 NADH regeneration and simultaneous benzylamine conversion along with CO2 fixation into HCOOH†","authors":"Kanchan Sharma, Rajesh K. Yadav, Rajesh K. Verma, Satyam Singh, Shaifali Mishra, Rehana Shahin, Atul P. Singh, Chandani Singh, Navneet K. Gupta, Jin-OoK Baeg, Hwanhui Yun and Hyung Joong Kim","doi":"10.1039/D4CY00825A","DOIUrl":"https://doi.org/10.1039/D4CY00825A","url":null,"abstract":"<p >Incorporating defects through intrinsic defect engineering has emerged as a versatile strategy for finely tuning the key properties of materials, particularly the redox capacity. Defects are fundamentally important in enhancement of the electronic, optical, and structural properties, thereby improving the photocatalytic effectiveness of a material. In this study, defects were induced in sulphur-doped graphitic carbon nitride through treatment with NaBH<small>₄</small>. This process notably enhanced the material's capacity to capture light, demonstrating the effectiveness of introducing defects to improve its performance. This work describes the photocatalytic action of defective S-doped g-C<small>₃</small>N<small>₄</small> (DSGN), where the surface electrons from the DSGN photocatalyst were directed to selectively reduce CO<small>₂</small> to formic acid while the holes assisted in the coupling of benzylamines. Notably, this process occured under the illumination of solar light without the need for any external sacrificial agent or bio-enzyme. The simultaneous conversion of benzylamines to their corresponding imines (94%) and CO<small>₂</small> transformation into HCOOH (203.46 mol g<small>_cat</small><small>⁻¹</small>) carried out under ordinary environmental conditions promoted by the DSGN photocatalyst make this a remarkable process. In addition to this, the DSGN photocatalyst showed a significant 1,4 NADH regeneration yield (75.40%) in 1 h. The recyclability and physico-chemical stability tests for DSGN demonstrated its high stability and suitability for repeated use. This work on photocatalysis utilizing the DSGN photocatalyst for both environmental remediation (CO<small>₂</small> reduction) and organic transformations (benzylamine coupling) in one step and exceptional 1,4 NADH regeneration capabaility has potential to contribute to the fields of green chemistry and sustainable energy.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7191-7204"},"PeriodicalIF":4.4,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798141","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":"Identification of Ni3Fe alloy as a candidate catalyst for quinoline selective hydrogenation with computations†","authors":"Zhaochun He, Yonghua Liu and Tao Wang","doi":"10.1039/D4CY01076K","DOIUrl":"https://doi.org/10.1039/D4CY01076K","url":null,"abstract":"<p >The 1,2,3,4-tetrahydroquinoline (py-THQL) is a crucial intermediate and fragment in chemical synthesis, but its production from quinoline (QL) selective hydrogenation in heterogeneous catalysis mainly relies on noble-metal-based catalysts. Therefore, the design of catalysts composed of earth-abundant elements for this reaction is meaningful. In this work, using density functional theory (DFT) calculations, we found the binding energy of QL to be a suitable descriptor to illustrate the general activity trend of metallic catalysts for QL hydrogenation. Among the screened bimetallic alloys composed of Fe, Co, Ni, and Cu, we computationally identified Ni<small>₃</small>Fe as a promising candidate catalyst with high stability, while our systematic mechanistic calculations showed the low energy barriers for each hydrogenation step. Our established DFT-based mean-field microkinetic model indicates a much higher turnover frequency for py-THQL production on the Ni<small>₃</small>Fe(111) surface than on the experimentally reported high-performance AuPd<small>₃</small>(111) surface. This work not only identified a valuable descriptor for the rational catalyst screening for the complex QL hydrogenation reaction but also theoretically predicted a cost-effective Ni<small>₃</small>Fe catalyst for the hydrogenation reaction.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7134-7139"},"PeriodicalIF":4.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798123","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":"Synergy of Ag and Pd in bimetallic catalysts for the selective oxidation of 5-(hydroxymethyl)furfural†","authors":"Dominik Neukum, Maya Eyleen Ludwig, Georgios Uzunidis, Ajai Raj Lakshmi Nilayam, Bärbel Krause, Silke Behrens, Jan-Dierk Grunwaldt and Erisa Saraçi","doi":"10.1039/D4CY01028K","DOIUrl":"https://doi.org/10.1039/D4CY01028K","url":null,"abstract":"<p >The synthesis of renewable bio-based monomers, like 2,5-furandicarboxylic acid (FDCA), is of high interest in the shift toward a circular economy. Bimetallic catalysts offer the variation of different properties, enabling the design of tailor-made catalysts. The combination of silver and palladium, both highly active for specific liquid-phase oxidation reactions, shows promise for superior performance in the selective oxidation of 5-(hydroxymethyl)furfural (HMF) to FDCA. While Ag/CBA and Ag<small>₃</small>Pd<small>₁</small>/CBA, supported on carbon black acetylene (CBA), were active only for the oxidation of the aldehyde group of HMF, increasing the Pd-fraction allowed for the oxidation of the alcohol group as well. In-depth characterization by X-ray diffraction, electron microscopy, and X-ray absorption spectroscopy revealed a synergistic effect between Ag and Pd in Pd-rich alloys, leading to an enhanced performance. Pd is particularly effective in activating oxygen, the oxidizing agent, while Ag ensures a high selectivity in the dehydrogenation reaction. Moreover, removing residual surfactants from the synthesized catalysts by increasing the calcination temperature further enhanced the activity. This study demonstrates the potential of tuning the catalytic properties of noble metal-based catalysts for optimizing liquid-phase oxidation reactions.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7163-7171"},"PeriodicalIF":4.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01028k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798126","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":"Correction: 1D Zn(ii)/2D Cu(i) halogen pyridyl coordination polymers. Band gap engineering by DFT for predicting more efficient photocatalysts in water treatment","authors":"Andrea García-Hernán, Fernando Aguilar-Galindo, Oscar Castillo and Pilar Amo-Ochoa","doi":"10.1039/D4CY90084G","DOIUrl":"https://doi.org/10.1039/D4CY90084G","url":null,"abstract":"<p >Correction for ‘1D Zn(<small>II</small>)/2D Cu(<small>I</small>) halogen pyridyl coordination polymers. Band gap engineering by DFT for predicting more efficient photocatalysts in water treatment’ by Andrea García-Hernán <em>et al.</em>, <em>Catal. Sci. Technol.</em>, 2024, https://doi.org/10.1039/d4cy00969j.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6720-6720"},"PeriodicalIF":4.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy90084g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598749","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}