Catalysis Today最新文献_第2页

Operando spectroscopic studies of alcohol to hydrocarbon process over HSSZ-13 with the aid of MCR-ALS analysis for active species identification 基于MCR-ALS分析的HSSZ-13上醇制烃过程的操作光谱研究

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-19 DOI: 10.1016/j.cattod.2025.115339

Anna Walczyk, Karolina A. Tarach, Agata Kordek, Agata Olszewska, Oliwia Rogala, Kinga Góra-Marek

{"title":"Operando spectroscopic studies of alcohol to hydrocarbon process over HSSZ-13 with the aid of MCR-ALS analysis for active species identification","authors":"Anna Walczyk, Karolina A. Tarach, Agata Kordek, Agata Olszewska, Oliwia Rogala, Kinga Góra-Marek","doi":"10.1016/j.cattod.2025.115339","DOIUrl":"10.1016/j.cattod.2025.115339","url":null,"abstract":"<div><div>This research examines the conversion of C<sub>1</sub> and C<sub>2</sub> alcohols to higher olefins utilizing protonic chabazite (HSSZ-13, SiAl = 11) zeolite. The study employs advanced <em>operando</em> spectroscopy techniques, including FT-IR and UV–vis, while simultaneously using mass spectrometry and gas chromatography to analyze the products. By applying identical amounts of C<sub>1</sub> and C<sub>2</sub> alcohols, the research can effectively examine the intermediates formed and coke production. Further, the same zeolite structure aids a more comprehensive understanding of reaction pathways. The <em>operando</em> FT-IR and UV–vis studies supplemented by mass spectrometry and gas chromatography results for products released from the catalyst surface provide significant information on the key intermediates involved. The similarities and discrepancies between the transformation of ethanol and methanol into olefins, according to the established hydrocarbon pool process, are noted. MCR-ALS analysis is employed for the <em>operando</em> FT-IR and UV–vis results, providing significant insights into the findings. Additionally, the research is supported by chromatographic examinations of the coke species obtained from spent catalysts.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"456 ","pages":"Article 115339"},"PeriodicalIF":5.2,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143873400","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}

引用次数: 0

Enhanced ammonia synthesis over barium cerate-supported cobalt catalyst by rare-earth element doping 通过掺杂稀土元素提高钡铈支撑钴催化剂的氨合成能力

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-17 DOI: 10.1016/j.cattod.2025.115342

Hubert Ronduda , Małgorzata Lemańska , Urszula Ulkowska , Wojciech Patkowski , Andrzej Ostrowski , Kamil Sobczak , Wioletta Raróg-Pilecka

{"title":"Enhanced ammonia synthesis over barium cerate-supported cobalt catalyst by rare-earth element doping","authors":"Hubert Ronduda , Małgorzata Lemańska , Urszula Ulkowska , Wojciech Patkowski , Andrzej Ostrowski , Kamil Sobczak , Wioletta Raróg-Pilecka","doi":"10.1016/j.cattod.2025.115342","DOIUrl":"10.1016/j.cattod.2025.115342","url":null,"abstract":"<div><div>A series of BaCeO<sub>3</sub> doped with various rare-earth elements (REE = Nd, Sm, Gd) were synthesised and used as the supports for cobalt catalysts for ammonia synthesis. The effects of rare-earth dopant type and concentration on the physicochemical properties and catalytic activities were studied using, e.g., XRD, STEM-EDX, and TPD techniques. Catalyst testing revealed that the optimal doping concentration was 10 mol%, regardless of the rare-earth ion. Samarium was identified as the most effective dopant, followed by gadolinium and neodymium. The superior performance of the Co/BaCe<sub>0.9</sub>REE<sub>0.1</sub>O<sub>3–</sub><sub>δ</sub> catalysts was due to the incorporation of REE dopant into the BaCeO<sub>3</sub> structure, which increased the electron density, enabling efficient electron transfer from the support to the Co surface. This, in turn, facilitated the N<sub>2</sub> dissociative adsorption, recognised as the rate-determining step (RDS) of ammonia synthesis. In addition, the catalysts were characterised by favourable hydrogen adsorption properties (co-existence of weak and strong adsorption sites), contributing to the effective hydrogen activation under the reaction conditions. This study provides an effective approach for designing cobalt catalysts supported on perovskites, demonstrating their great potential as next-generation catalysts for ammonia synthesis.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"456 ","pages":"Article 115342"},"PeriodicalIF":5.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851536","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}

引用次数: 0

One-pass conversion of syngas to BTX/para-xylene aromatics over tandem oxide-zeolite catalysts based on large crystal size HZSM-5 基于大晶粒HZSM-5的串联氧化物-沸石催化剂上合成气一次转化为BTX/对二甲苯芳烃

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-17 DOI: 10.1016/j.cattod.2025.115340

Raúl Murciano, M. Teresa Navarro, Agustín Martínez

{"title":"One-pass conversion of syngas to BTX/para-xylene aromatics over tandem oxide-zeolite catalysts based on large crystal size HZSM-5","authors":"Raúl Murciano, M. Teresa Navarro, Agustín Martínez","doi":"10.1016/j.cattod.2025.115340","DOIUrl":"10.1016/j.cattod.2025.115340","url":null,"abstract":"<div><div>The one-pass conversion of renewable syngas into aromatics, particularly to BTX (benzene, toluene, xylenes) and <em>para</em>-xylene (PX), represents a promising approach to produce high-value sustainable chemicals from non-fossil resources. In this work, a systematic study of the modification of HZSM-5 zeolite by surface silylation and incorporation of MgO was performed aiming at maximising the BTX and PX selectivity in the syngas-to-aromatics (STA) reaction using tandem Zn-ZrO<sub>2</sub>+HZSM-5 catalysts following the methanol route. A zeolite with unusually large crystal size was purposedly used to intensify the <em>shape selectivity</em> effect. This zeolite exhibited high BTX selectivity (53.0 % in aromatics) albeit poor stability with TOS. Generation of a proper amount of mesopores via controlled desilication improved the catalyst stability and the aromatics selectivity (from 59.2 % up to 73.2 %) at the cost of lowering the BTX selectivity. Effective passivation of the external Brønsted acid sites was reached by submitting the mesoporous zeolite to four silylation cycles with TEOS. The silylation treatment significantly raised the BTX selectivity to 52.1 % while maintaining high selectivity of total aromatics (67.9 %), but had only a moderate positive effect on PX selectivity. Incorporation of Mg species in the silylated zeolite produced the largest impact on PX selectivity, attaining an outstanding value of 76.8 % in xylenes (41.2 % in aromatics) upon loading 3 wt% Mg.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"456 ","pages":"Article 115340"},"PeriodicalIF":5.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143860441","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}

引用次数: 0

Six-lump kinetic model for plastic pyrolysis oil (PPO) and vacuum gasoil (VGO) blend hydroprocessing considering selective catalyst deactivation 考虑选择性催化剂失活的塑料热解油（PPO）和真空汽油（VGO）共混加氢过程的六块动力学模型

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-15 DOI: 10.1016/j.cattod.2025.115341

Suní Rodríguez , David Trueba , Mario Escribano , José M. Arandes , Roberto Palos , Alazne Gutiérrez

{"title":"Six-lump kinetic model for plastic pyrolysis oil (PPO) and vacuum gasoil (VGO) blend hydroprocessing considering selective catalyst deactivation","authors":"Suní Rodríguez , David Trueba , Mario Escribano , José M. Arandes , Roberto Palos , Alazne Gutiérrez","doi":"10.1016/j.cattod.2025.115341","DOIUrl":"10.1016/j.cattod.2025.115341","url":null,"abstract":"<div><div>A six-lump kinetic model has been developed for the hydroprocessing of a mixture of vacuum gas oil (VGO) and plastic pyrolysis oil (PPO) in a ratio of 90:10 wt%, using a NiW/HY catalyst. This process aims to valorize waste plastics by producing valuable oil fractions such as naphtha and light cycle oil (LCO). The experiments were conducted in a semi-continuous stirred tank reactor across a temperature range of 370–440 °C and under 80 bar hydrogen pressure. Special attention was given on developing models to quantify the deactivation effects caused by coke and metal (Fe) deposition, with the latter having a lesser impact. These models are based on experimentally validated mechanisms of these phenomena, investigated through different <em>post-mortem</em> characterization techniques applied to spent catalysts. The successful fit of a separable deactivation model –featuring different deactivation functions for each reaction lump and an activity function related to the coke content– highlights the significant impact of pore blocking due to coke deposition. This blocking selectively affects the diffusion of molecules within the different lumps, depending on their volume. The results indicate that increasing the temperature has a favorable effect on the yield of naphtha and LCO fractions. At 440 °C and 180 min, the yield of these lumps exceeds 70 wt%, with a conversion greater than 75 %. Notably, at this elevated temperature, the hydrocracking of coke components becomes more favorable mitigating the deactivation caused by coke deposition.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"457 ","pages":"Article 115341"},"PeriodicalIF":5.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143887354","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}

引用次数: 0

Evaluation of the performance and detection of the oxygen reduction reaction kinetics of metal doped imine framework in proton exchange membrane fuel cells 质子交换膜燃料电池中金属掺杂亚胺骨架的性能评价及氧还原反应动力学检测

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-14 DOI: 10.1016/j.cattod.2025.115320

Álvaro Tolosana-Moranchel , Nicolas Bibent , José Luis Gómez de la Fuente , Moulay Tahar Sougrati , Frédéric Jaouen , Diego Gianolio , María Retuerto , Sergio Rojas

{"title":"Evaluation of the performance and detection of the oxygen reduction reaction kinetics of metal doped imine framework in proton exchange membrane fuel cells","authors":"Álvaro Tolosana-Moranchel , Nicolas Bibent , José Luis Gómez de la Fuente , Moulay Tahar Sougrati , Frédéric Jaouen , Diego Gianolio , María Retuerto , Sergio Rojas","doi":"10.1016/j.cattod.2025.115320","DOIUrl":"10.1016/j.cattod.2025.115320","url":null,"abstract":"<div><div>Fe/N/C based catalysts are the best positioned ones to replace the state-of-the-art Pt-based catalysts for the oxygen reduction reaction (ORR) in Proton Exchange Membrane Fuel Cells (PEMFCs). Here, a Fe/N/C catalyst characterized by a high N/C ratio, has been synthesized from the pyrolysis of a N-rich imine-based polymer. In acidic electrolyte (0.1 M HClO<sub>4</sub>) the catalyst demonstrates notable ORR activity with E<sub>onset</sub> and E<sub>1/2</sub> values of 1.09 and 0.77 V vs. RHE, respectively. Furthermore, the catalyst’s performance has been assessed in a single cell PEMFC setup. The optimization of the membrane electrode assembly (MEA) with the Fe/N/C catalyst entails examining various ionomer to catalyst ratios (I/C) as well as two coating methods: spray coating and drop casting. The optimized MEA achieved a cell performance of 725 mA cm<sup>−2</sup> at 0.3 V and a power density close to 220 mW cm<sup>−2</sup>. In order to understand the factors influencing PEMFC polarisation curves, electrochemical impedance spectroscopy (EIS) was performed under potentiostatic conditions. The effect of operational parameters, such as ionomer to catalyst ratios (I/C) and the use of either O<sub>2</sub> or air at the anode feed, has been investigated. EIS spectra allow the calculation of the distribution of relaxation times (DRT), providing insights into the rate and resistance of the ORR process occurring at the MEA. Notably, the cathode with an I/C= 2, prepared by drop casting, exhibited superior performance attributed to reduced ORR resistances. The current density and power density reached with the 25 cm<sup>2</sup> MEA are comparable to those obtained with the 5 cm<sup>2</sup> MEA using O<sub>2</sub> as cathode reactant.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"456 ","pages":"Article 115320"},"PeriodicalIF":5.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143860440","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}

引用次数: 0

Multifunctional CaBi LDH/Ag-gC3N4 catalytic composite for sustainable pollution remediation and photochemical conversion into usable derivatives 多功能 CaBi LDH/Ag-gC3N4 催化复合材料用于可持续污染修复和光化学转化为可用衍生物

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-12 DOI: 10.1016/j.cattod.2025.115315

Prabagar Jijoe Samuel , Challaraj Emmanuel E S , Vinod Divya , Mohammad Khalid , Mohammed H. Alqarni , Harikaranahalli Puttaiah Shivaraju

{"title":"Multifunctional CaBi LDH/Ag-gC3N4 catalytic composite for sustainable pollution remediation and photochemical conversion into usable derivatives","authors":"Prabagar Jijoe Samuel , Challaraj Emmanuel E S , Vinod Divya , Mohammad Khalid , Mohammed H. Alqarni , Harikaranahalli Puttaiah Shivaraju","doi":"10.1016/j.cattod.2025.115315","DOIUrl":"10.1016/j.cattod.2025.115315","url":null,"abstract":"<div><div>A simple methodology was devised for synthesizing the CaBi LDH/Ag-gC<sub>3</sub>N<sub>4</sub> composite using eggshell-derived calcium. Composite is a potent catalyst for converting atmospheric gases into value-added derivatives and photocatalytic remediation with antimicrobial potential. An innovative CaBi LDH/Ag-gC<sub>3</sub>N<sub>4</sub> was effectively fabricated using solvothermal and hydrothermal techniques and was subjected to sophisticated characterizations. Enhanced crystallinity with the intact framework of Ag-gC<sub>3</sub>N<sub>4</sub> into CaBi LDH, agglomerated cloud-like structure, easy electron mobility transfer with extensive charge separation and high photocatalysis have been confirmed by characterization studies. The CaBi LDH/Ag-gC<sub>3</sub>N<sub>4</sub> composite further demonstrated photocatalytic conversion of N<sub>2</sub> and CO<sub>2</sub> into NH<sub>3</sub> (up to 84.02 µmol/L at 45 min) and functional hydrocarbon derivatives (C<sub>2</sub>H<sub>6</sub>O ∼350 μmol/L and CH<sub>3</sub>OH ∼118.2 μmol/L at 4 hr) respectively under visible light. The composite demonstrated superior photocatalytic remediation of ciprofloxacin (CPF) under visible spectrum and antibacterial efficacy against two pathogens, <em>Escherichia coli and Staphylococcus aureus</em>, supported by well suggested mechanism. The photoreduction mechanism of CaBi LDH/Ag-gC<sub>3</sub>N<sub>4</sub> is discussed, and the CB position of g-C<sub>3</sub>N<sub>4</sub> (-1.16 eV) showed comparatively having lesser value (negative) than CB of CaBi LDH (-0.73 eV). An intricate mechanism has been devised in each photocatalytic reaction to elucidate the general reactions in line with the intended reactions.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"455 ","pages":"Article 115315"},"PeriodicalIF":5.2,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835374","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}

引用次数: 0

Addressing the influence of alkaline compounds in 5-hydroxymethylfurfural oxidation and separation towards 2,5-furandicarboxylic acid 探讨碱性化合物对5-羟甲基糠醛氧化分离制备2,5-呋喃二羧酸的影响

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-12 DOI: 10.1016/j.cattod.2025.115338

P. Díaz-Maizkurrena , J. Requies , A. Iriondo , M. Macías-Villasevil

{"title":"Addressing the influence of alkaline compounds in 5-hydroxymethylfurfural oxidation and separation towards 2,5-furandicarboxylic acid","authors":"P. Díaz-Maizkurrena , J. Requies , A. Iriondo , M. Macías-Villasevil","doi":"10.1016/j.cattod.2025.115338","DOIUrl":"10.1016/j.cattod.2025.115338","url":null,"abstract":"<div><div>The conversion of 5-hydroxymethylfurfural (HMF) into valuable chemicals is a critical challenge in biomass valorization. This study explores the degradation of HMF in the presence of various alkaline compounds (KOH, NaOH, Na<sub>2</sub>CO₃, and NaHCO<sub>3</sub>) without the use of a catalyst. The experiments showed that strong bases such as KOH and NaOH significantly accelerated HMF degradation, even under cold storage conditions, while weaker bases (Na<sub>2</sub>CO<sub>3</sub> and NaHCO<sub>3</sub>) exhibited slower degradation rates. Additionally, the aerobic oxidation of HMF to 2,5-furandicarboxylic acid (FDCA) was evaluated using a Pt-Bi/C catalyst under different alkaline conditions. Results indicated that the type and strength of the alkaline compound strongly influenced FDCA yield, with intermediate bases such as Na<sub>2</sub>CO<sub>3</sub> providing the highest yields (up to 99.3 %). The study also examined the post-reaction addition of alkaline compounds, revealing that this step is essential for dissolving FDCA, which may precipitate as a solid under acidic conditions. Two methods for FDCA separation and recovery were assessed: precipitation with HCl and dissolution in isopropanol. Both methods proved effective, with the HCl method yielding crystalline FDCA and isopropanol offering a more environmentally friendly alternative. These findings provide valuable insights into optimising reaction conditions for HMF valorization and improving FDCA recovery processes.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"456 ","pages":"Article 115338"},"PeriodicalIF":5.2,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143873399","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}

引用次数: 0

Ethane ODH with CO2 over alumina-supported Fe-Ni-O mixed oxides catalysts 乙烷ODH与CO2在氧化铝负载的Fe-Ni-O混合氧化物催化剂上的反应

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-11 DOI: 10.1016/j.cattod.2025.115317

Gustavo do N. Franceschini , Patricia Concepcion , Marcio Schwaab , Joaquín Martínez-Triguero , José M. Lopez Nieto

{"title":"Ethane ODH with CO2 over alumina-supported Fe-Ni-O mixed oxides catalysts","authors":"Gustavo do N. Franceschini , Patricia Concepcion , Marcio Schwaab , Joaquín Martínez-Triguero , José M. Lopez Nieto","doi":"10.1016/j.cattod.2025.115317","DOIUrl":"10.1016/j.cattod.2025.115317","url":null,"abstract":"<div><div>The dehydrogenation of ethane in the presence of CO<sub>2</sub> on alumina supported Fe-Ni-O catalysts was studied. The Fe/Ni ratio in catalysts strongly influences both the conversion of ethane and CO<sub>2</sub> and the nature of reaction products. Iron species, linked to the hematite phase (α-Fe<sub>3</sub>O<sub>4</sub>), favors ethane ODH but also the RWGS and dry reforming reactions (as parallel reactions). Nickel oxide has a high catalytic activity due to its capacity to break both C-H and C<img>C bonds in a non-selective way, facilitating the generation of CO. Characterization results show changes in catalysts during the reaction. The H<sub>2</sub>-TPR patterns of catalysts suggest a low interaction between the support and the iron particles, and a parallelism between the reducibility of iron particles and the conversion of reactants. In addition, all catalysts suffer important restructuration under reaction conditions, with iron oxide segregates to the catalyst surface together with a partial reduction of Fe<sup>3</sup><sup>+</sup> to Fe<sup>2+</sup> (as determined by XPS). These changes could be confirmed by XRD, Raman, XPS and UV–vis spectroscopy analyses. Temperature programmed surface reactions (TPSR), under different experimental conditions, indicate an important role of nickel in the bimetallic catalysts, avoiding severe reduction of the catalyst and stabilizing different types of iron oxide species with different selectivity to products.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"455 ","pages":"Article 115317"},"PeriodicalIF":5.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843702","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}

引用次数: 0

Influence of CO2 presence on propane conversion routes over Cr- and Ga-doped PtCe/Al2O3 catalysts CO2存在对Cr和ga掺杂PtCe/Al2O3催化剂丙烷转化路线的影响

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-11 DOI: 10.1016/j.cattod.2025.115318

D. Ballesteros-Plata , I. Barroso-Martín , J.A. Cecilia , P. Concepción , J.M. López Nieto , E. Rodríguez-Castellón , A. Infantes-Molina

{"title":"Influence of CO2 presence on propane conversion routes over Cr- and Ga-doped PtCe/Al2O3 catalysts","authors":"D. Ballesteros-Plata , I. Barroso-Martín , J.A. Cecilia , P. Concepción , J.M. López Nieto , E. Rodríguez-Castellón , A. Infantes-Molina","doi":"10.1016/j.cattod.2025.115318","DOIUrl":"10.1016/j.cattod.2025.115318","url":null,"abstract":"<div><div>A set of catalysts containing Cr- or Ga-doped Pt-CeO<sub>2</sub> supported on alumina (PCA, Cr-PCA and Ga-PCA) were synthesized by incipient wetness impregnation and tested in propane conversion processes. The catalysts were studied in the propane conversion process with or without CO<sub>2</sub> in the feed. In all cases, an enhancement in stability was found when CO<sub>2</sub> was present in the reaction medium despite the lower catalytic activity. As well, all catalysts presented a higher propylene selectivity in the absence of CO<sub>2</sub>, indicating that the direct dehydrogenation of propane is the main reaction route. Moreover, CO<sub>2</sub>-assisted propane cracking to ethylene is favoured over propane reforming or direct cracking, given the minimal selectivity to other products like methane. With regards to the catalyst composition, Cr-PCA catalyst was the most active catalyst both in the absence and presence of CO<sub>2</sub>, due to the presence of weak acidity and coexistence of Cr<sup>3 +</sup> and Cr<sup>6+</sup> redox species, as evidenced by XPS analysis. Ga-PCA catalyst was more selective to propylene, indicating that higher acidity of weak-to-medium nature along with formation of low coordinated Ga<sup>3+</sup> species is beneficial for the CO<sub>2</sub>-ODH process. Raman, DTG and XPS analyses after reaction with CO<sub>2</sub> showed that the deactivation of the catalysts was mainly due to carbon deposits of amorphous and graphitic nature on the surface of the catalysts.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"455 ","pages":"Article 115318"},"PeriodicalIF":5.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835372","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}

引用次数: 0

Improved productivity in direct dimethyl ether synthesis and sorption enhanced DME synthesis using tungstosilicic acid as the acidic function 提高了直接二甲醚的合成效率，并以钨硅酸为酸性功能，吸附增强了二甲醚的合成

IF 5.2 2区化学

Catalysis Today Pub Date : 2025-04-11 DOI: 10.1016/j.cattod.2025.115319

Cristina Peinado , Dalia Liuzzi , Jurriaan Boon , Sergio Rojas

{"title":"Improved productivity in direct dimethyl ether synthesis and sorption enhanced DME synthesis using tungstosilicic acid as the acidic function","authors":"Cristina Peinado , Dalia Liuzzi , Jurriaan Boon , Sergio Rojas","doi":"10.1016/j.cattod.2025.115319","DOIUrl":"10.1016/j.cattod.2025.115319","url":null,"abstract":"<div><div>Renewable dimethyl ether (DME) can reduce the carbon footprint in LPG and transportation sectors. The direct synthesis of DME (DDMES) is attracting a great deal of attention because it is possible to increase the productivity of DME. However, DDMES is hindered by the formation of a high amount of water, which promotes the deactivation of both catalytic phases used in the DDMES, namely Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> and γ-Al<sub>2</sub>O<sub>3</sub>. This is particularly relevant when CO<sub>2</sub>-rich syngas is used, since it leads to a higher production of H<sub>2</sub>O. In this work we show that heteropolyacids such as HSiW are a suitable alternative to state-of-the-art γ-Al<sub>2</sub>O<sub>3</sub> for the dehydration of methanol during the DDMES. This is because HSiW is not deactivated by the presence of water in the reaction medium. Thus, catalytic beds with HSiW reach up to four times higher DME productivity than those containing γ-Al<sub>2</sub>O<sub>3</sub>. This feature is further exacerbated when water is removed from the reactor by means of a sorbent, i.e., during the sorption enhanced direct DME synthesis (SEDMES). Thus, the total carbon conversion is higher for SEDMES than for DDMES regardless of the actual nature of the acid catalyst.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"455 ","pages":"Article 115319"},"PeriodicalIF":5.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829756","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}

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