Catalysis Science & Technology最新文献

{"title":"Construction of a highly efficient MoS2-based composite electrocatalyst for the oxygen evolution reaction†","authors":"Mengyan Huang, Bo Liu, Junwei Wu, Junfeng Gu, Yichen Zheng, Peiyan Ma, Bei Li and Zhengyi Fu","doi":"10.1039/D4CY00923A","DOIUrl":"https://doi.org/10.1039/D4CY00923A","url":null,"abstract":"<p >Molybdenum disulfide (MoS<small>₂</small>) has great potential for the catalysis of the oxygen evolution reaction (OER) due to its suitable valence band edge. However, the high adsorption energy barriers of the key intermediates *OH and *OOH at the catalytic sites severely limit its catalytic activity. In this research, we designed a carboxyl-decorated MoC@MoS<small>₂</small> composite (CC-MoC@MoS<small>₂</small>) electrocatalyst for OER, in which the S sites of MoS<small>₂</small> provide effective adsorption of the two intermediates. The optimized CC-MoC@MoS<small>₂</small> could catalyze OER rapidly and stably, reaching current densities of 10, 50 and 100 mA cm<small>⁻²</small> in alkaline medium at overpotentials of 248, 307 and 359 mV, respectively.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6380-6392"},"PeriodicalIF":4.4,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524259","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":"Oxygen vacancy-dependent low-temperature performance of Ni/CeO2 in CO2 methanation†","authors":"Luliang Liao, Kunlei Wang, Guangfu Liao, Muhammad Asif Nawaz and Kun Liu","doi":"10.1039/D4CY00679H","DOIUrl":"https://doi.org/10.1039/D4CY00679H","url":null,"abstract":"<p >The transformative power of CO<small>₂</small> methanation can efficiently transform greenhouse gases into high-value products, aligning with the carbon neutrality goals. However, achieving this target at low temperature requires cumbersome efforts in designing catalysts that possess high reactivity and selectivity. Focusing on understanding the pivotal role of alkaline (such as Ca) sites in catalyzing these reactions at lower temperature could be a way of strategically creating oxygen vacancies with varying activity gradients. Designing CaCe-SG <em>via</em> a sol–gel method in the current study to integrate Ca into the CeO<small>₂</small> lattice marked the highly active moderate-strength alkaline centers which resulted in the intrinsic activity soaring by an impressive 400% compared to the conventional Ni/CeO<small>₂</small> catalysts. Supported by H<small>₂</small>-TPD, Raman, and XPS analyses, a crucial revelation was unveiled where Ca modification induced a surge in the dispersion of active Ni species on Ni/CaCe-SG catalysts, thereby enhancing the abundant surface oxygen vacancies. <em>In situ</em> infrared spectroscopy further confirmed that the modified catalyst diligently followed the reaction pathway of CO<small>₃</small>H* → HCOO* → CH<small>₄</small>, culminating in the CO<small>₂</small> methanation activity with a low-temperature catalyst <em>via</em> the meticulous optimization of synthesis methods that propelled the process forward to the anticipated oxygen vacancy-induced moderate-strength alkaline centers.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6537-6549"},"PeriodicalIF":4.4,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598706","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":"Fundamental studies of ruthenium species supported on boron nitride nanotubes: metal loading and pretreatment effects on CO oxidation†","authors":"Jinwon Choi, Amol Pophali, Byeongseok Kim, Kwangsuk Yoon, Thomas You-Seok Kim, Hocheol Song, Sang Eun Shim, Jaewoo Kim and Taejin Kim","doi":"10.1039/D4CY00945B","DOIUrl":"https://doi.org/10.1039/D4CY00945B","url":null,"abstract":"<p >Multiwalled boron nitride nanotube (BNNT), as a catalyst support, has become one of the promising materials due to its high oxidation resistance and thermal stability. In this work, ruthenium (Ru) supported on BNNT catalysts with different metal loadings and treatment conditions was investigated for CO oxidation as a model reaction. To understand the physicochemical properties of the prepared samples, a suite of techniques, including FTIR, UV-Raman, SEM, TEM, and XPS, was utilized. The results showed that the RuO<small>_<em>x</em></small> species were located on both the interior and the exterior surfaces of the BNNT, and an increase in metal loading led to increased active sites. 1 wt% RuO<small>_<em>x</em></small>/BNNT (oxidized) exhibited better catalytic activity than 1 wt% Ru/BNNT (reduced), indicating that treatment conditions significantly affect the catalytic properties. Reaction conditions, such as GHSV and the O<small>₂</small>/CO ratio, were varied to further investigate the external mass transfer limitations and reaction mechanism of the 1 wt% RuO<small>_<em>x</em></small>/BNNT catalyst. The peculiar tubular morphology of the BNNT resulted in negligible external mass transfer limitation, and the catalyst might primarily follow the Eley–Rideal (ER) mechanism over the Langmuir–Hinshelwood (LH) mechanism.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6198-6206"},"PeriodicalIF":4.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524272","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":"High-temperature calcination enhances the activity of MnOx catalysts for soot oxidation†","authors":"Meng Wang, Jingyi Wang, Yan Zhang, Yunbo Yu and Wenpo Shan","doi":"10.1039/D4CY00983E","DOIUrl":"https://doi.org/10.1039/D4CY00983E","url":null,"abstract":"<p >High-temperature calcination usually induces the sintering of catalysts, thus resulting in negative effects on their performance. However, in this study we surprisingly found that high-temperature calcination could enhance the activity of MnO<small>_<em>x</em></small> catalysts for soot oxidation. Combined experimental and theoretical analysis revealed that high-temperature calcination of MnO<small>_<em>x</em></small> (900 °C) could induce the generation of more oxygen defects, due to the transformation of α-MnO<small>₂</small> to δ-MnO<small>₂</small> and Mn<small>₂</small>O<small>₃</small>, with lower formation energy for oxygen defects. The generated oxygen defects would facilitate activation of surface chemisorbed oxygen, producing more active oxygen species, which can further oxidize NO to NO<small>₂</small> to accelerate soot combustion. Therefore, MnO<small>_<em>x</em></small> calcinated at 900 °C exhibited much higher activity for soot oxidation than that calcinated at 500 °C. This study provides significant insight into the effects of calcination temperature on MnO<small>_<em>x</em></small> catalysts, thereby aiding in the design of high-efficiency catalysts for the control of soot emission.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6278-6285"},"PeriodicalIF":4.4,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00983e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524284","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":"Modification of porous bismuth molybdate for high removal of antibiotics and H2O2 production†","authors":"Shilin Li, Yunhui Tian and Guangxin Zhang","doi":"10.1039/D4CY00906A","DOIUrl":"https://doi.org/10.1039/D4CY00906A","url":null,"abstract":"<p >The regulations of the Bi<small>₂</small>MoO<small>₆</small> structure, such as dopant incorporation, composite formation, and synthesis condition modification, have garnered significant attention due to their implications for enhancing photocatalytic activity. In this study, potassium acetate was introduced into the synthesis of Bi<small>₂</small>MoO<small>₆</small><em>via</em> a one-pot hydrothermal method to augment its photocatalytic efficiency. It was observed that the addition of potassium acetate effectively modulated the microstructure of Bi<small>₂</small>MoO<small>₆</small>. XRD and XPS analyses confirmed the incorporation of K<small>⁺</small> ions into the [MoO<small>₄</small>]<small>²⁻</small> and [Bi<small>₂</small>O<small>₂</small>]<small>²⁺</small> layers, significantly influencing the phase structure and morphology of Bi<small>₂</small>MoO<small>₆</small>. Controlled addition of potassium acetate improved the dispersibility of Bi<small>₂</small>MoO<small>₆</small>, whereas excessive amounts led to a phase transition from Bi<small>₂</small>MoO<small>₆</small> to Bi<small>_3.64</small>Mo<small>_0.36</small>O<small>_6.55</small>. The antibiotic degradation rate and H<small>₂</small>O<small>₂</small> yield were used to evaluate the catalytic performance of the catalyst. Bi<small>₂</small>MoO<small>₆</small> modified with potassium acetate exhibited higher photocatalytic efficiency than unmodified Bi<small>₂</small>MoO<small>₆</small>. Specifically, the optimal BMO-1 sample exhibited 97.7% CIP degradation within 15 min of illumination. The enhanced adsorption efficiency was primarily attributed to the effective dispersion and the presence of mesopores. Furthermore, the introduction of oxygen vacancies and improved photogenerated carrier separation efficiency contributed to enhanced photocatalytic performance. This study introduces a novel method for structurally tuning bismuth molybdate.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6420-6429"},"PeriodicalIF":4.4,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524291","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":"Hydrolysis of ammonia borane for green hydrogen production over a Pd/C3N4 nanocatalyst synthesized by electron beam irradiation†","authors":"Manish Shingole, Seemita Banerjee, Priyanka Ruz, Asheesh Kumar, Pratibha Sharma and V. Sudarsan","doi":"10.1039/D4CY00761A","DOIUrl":"10.1039/D4CY00761A","url":null,"abstract":"<p >Ammonia borane (AB), which possesses a theoretical hydrogen storage capacity of 19.6 wt%, is extensively examined to tackle solid state hydrogen storage challenges. In this paper, we present a strategy to synthesize Pd dispersed g-C<small>₃</small>N<small>₄</small> by decorating different concentrations of Pd on the g-C<small>₃</small>N<small>₄</small> matrix by electron beam irradiation process. Catalyst characterization reveals successful formation of g-C<small>₃</small>N<small>₄</small> supported highly dispersed face-centred cubic nanocrystalline Pd, with a particle size of less than 10 nm. The catalyst performance for AB hydrolysis exhibits an activation energy of 27.36 kJ mol<small>⁻¹</small>, surpassing many Pd-based catalysts. Successive hydrolysis experiments and detailed analysis of the spent catalyst establish the reusability and stability of the catalyst. The study shows that though the initial AB concentration does not affect the hydrolysis reaction rate, addition of impurity ions to the reaction media can significantly modify it. Detailed mechanistic investigation by the kinetic isotope effect, time dependent FT-IR, and mass spectrometry clarifies that the evolved hydrogen from the AB hydrolysis reaction comes from both the breakage of the B–H bond and hydrogen from the solvent. Activation of the O–H bond of the solvent due to the adsorption on the catalyst surface plays a significant role in the AB hydrolysis reaction and comprises the rate-determining step.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6338-6350"},"PeriodicalIF":4.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260022","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":"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/D4CY00969J","DOIUrl":"https://doi.org/10.1039/D4CY00969J","url":null,"abstract":"<p >One of the key factors determining the photocatalytic capacity of a compound is its optical band gap, which, within an optimal range, maximizes the absorption and utilization of solar light. Recent research shows that modifying organic ligands and metal centers in metal–organic frameworks (MOFs) plays a crucial role in tailoring specific band gap characteristics. Many research articles use different structural MOF motives for photocatalysis, but few delve into band gap engineering using quantum chemistry calculations. Density functional theory (DFT) has been widely used to understand the possible mechanisms of action of some photocatalysts, but few studies directly relate the band gap to the ligands present in the compounds. In our study, DFT calculations are used to get a deeper understanding of the relationship between crystal and band structures aimed at predicting and enhancing the photocatalytic properties of new isostructural coordination polymers (CPs) with the general formula [ZnX<small>₂</small>(L)<small>₂</small>]<small>_<em>n</em></small> or [Cu<small>₂</small>X<small>₂</small>(L)]<small>_<em>n</em></small> from X = Cl and Br to X = I, and from 1,2-bis(4-pyridyl) ethane (BPE) to 1,2-bis(4-pyridyl)ethylene (BPEE) offering significant time and cost savings by enabling predictions. Despite the good band gap value of [ZnI<small>₂</small>(BPEE)<small>₂</small>]<small>_<em>n</em></small>, all members of the Zn/BPEE family show partial hydrolysis in water, which limits their use as photocatalysts. However, the 2D [Cu<small>₂</small>X<small>₂</small>(BPEE)]<small>_<em>n</em></small> (X= Cl, Br, and I) CPs are more insoluble and stable in water. Following the DFT results, the study of [Cu<small>₂</small>I<small>₂</small>(BPEE)]<small>_<em>n</em></small> as photocatalysts with water-persistent organic dyes (methylene blue (MB), methyl orange (MO), and tartrazine (Trz)) has been done. This approach allows us to assess whether the experimental synthesis of novel compounds with improved optical properties is worthwhile for their potential use as heterogeneous photocatalysts for water remediation.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6573-6583"},"PeriodicalIF":4.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00969j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598735","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":"Heterogeneous oxidative upcycling of polystyrene plastics to benzoic acid under air conditions†","authors":"Chengyang Sun, Yong Guo, Xiaohui Liu and Yanqin Wang","doi":"10.1039/D4CY00970C","DOIUrl":"https://doi.org/10.1039/D4CY00970C","url":null,"abstract":"<p >Plastics with inter-monomer C–C bond linkages comprise more than 70% of all plastics production, but their chemical recycling and upcycling usually require harsh conditions due to the inertness of C–C bonds, hindering their utilization efficiency. Here, we develop an oxidative upcycling strategy to convert polystyrene (PS) waste into benzoic acid over a NiO/TiO<small>₂</small> catalyst. This system is carried out in an environmentally friendly manner in an aqueous phase by using air as the oxidant, and up to 51.1% carbon yield of benzoic acid is obtained at 200 °C, 1 MPa air and 18 h. The conversion of real-life PS plastics is also successfully demonstrated. The reaction mechanism is further investigated by capturing radicals and intermediates during the oxidative reaction, confirming ·O<small>₂</small><small>⁻</small> radicals as the reactive oxygen species. A possible oxidative mechanism was proposed: the ·O<small>₂</small><small>⁻</small> radicals first activated the C–H bonds in the aliphatic portion of PS to generate carbonyl groups or C<img>C bonds; then, through attack of the weak C<img>C bonds, the polymer was constantly depolymerized to smaller oxygenated oligomers, dimers and finally the target product, benzoic acid. This work has provided a promising and green polystyrene upcycling strategy.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6584-6591"},"PeriodicalIF":4.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598736","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":"Heterostructure engineered construction of N-doped CuO@Co3O4 for highly efficient electrocatalytic reduction of nitrate to ammonia†","authors":"Shi-Jiao Dong, Sai Huang, Ao Wang, Yan Meng, Gang Xu and Jun-Ling Song","doi":"10.1039/D4CY00905C","DOIUrl":"https://doi.org/10.1039/D4CY00905C","url":null,"abstract":"<p >The electrochemical reduction of nitrate can be a promising and sustainable alternative for the industrially used, energy-intensive Haber–Bosch process under mild conditions and also solve the issue of nitrate nitrogen pollution in water. We present here the facile construction of an N-doped CuO@Co<small>₃</small>O<small>₄</small>/NF nanoarray on nickel foam for highly efficient NH<small>₃</small> electrosynthesis <em>via</em> selective NO<small>₃</small><small>⁻</small> reduction in neutral electrolyte. At −0.85 V (<em>versus</em> the reversible hydrogen electrode (RHE)), this N-doped CuO@Co<small>₃</small>O<small>₄</small>/NF nanoarray obtained an outstanding Faraday efficiency (FE) of 99.78% and NH<small>₃</small> yield of up to 31.92 mg h<small>⁻¹</small> cm<small>⁻²</small> when operated in 0.1 M phosphate buffer solution with added 50 mM NaNO<small>₃</small>. In addition, its excellent electrochemical performance was maintained for at least 12 h. Furthermore, according to the characterization, the enhanced electrocatalytic performance could be attributed to the synergistic effect of N-dopant and relatively large amounts of Co(<small>II</small>) and oxygen vacancies (OVs) in the heterostructure, leading to the suppression of the hydrogen evolution reaction (HER) and the improvement of electron/mass transfer at the N-doped CuO@Co<small>₃</small>O<small>₄</small>/NF heterostructure.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6372-6379"},"PeriodicalIF":4.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524258","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":"Multivalent cobalt nanoparticles supported on silica for efficient and sustainable methanolysis of commercial polyethylene terephthalate waste bottles†","authors":"Kamlesh Kumari ,&nbsp;Priyanka Choudhary ,&nbsp;Venkata Krishnan","doi":"10.1039/d4cy00468j","DOIUrl":"10.1039/d4cy00468j","url":null,"abstract":"<div><div>Plastic waste management is a huge challenge in today's world wherein polyethylene terephthalate (PET) is one of the major contributors. Chemical upcycling of plastic waste into valuable chemicals is one of the most effective methods for plastic waste management. In this work, multivalent cobalt nanoparticles supported on silica were used as a heterogeneous catalyst for the methanolysis of PET under mild reaction conditions, wherein PET was converted into dimethyl terephthalate (DMT) as the major product in the presence of methanol. In this PET methanolysis process, the effects of various reaction parameters, such as reaction time, temperature, cobalt loading on silica and catalyst amount on the conversion of PET and the yield of DMT were investigated. The developed catalyst results in significantly high DMT yield and PET conversion under mild reaction conditions. To investigate the heterogeneous nature of the developed catalyst, recyclability studies were performed which show excellent reusability with good conversion and product yield. Thus, multivalent cobalt nanoparticles supported on silica have the advantage of good conversion efficiency, high product yield, nontoxicity, excellent recyclability, and ease of separation for the methanolysis of PET. This work is anticipated to open new avenues in the field of plastic upcycling.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 18","pages":"Pages 5352-5363"},"PeriodicalIF":4.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141880531","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}