Catalysis Today最新文献

英文中文

Influence of operating conditions on the kinetics of Iron-catalysed gasification of biocarbons with CO2

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-28 DOI: 10.1016/j.cattod.2025.115289

D. Chaos-Hernández, N. Latorre, P. Tarifa, E. Romeo, A. Monzón

In this study, we investigated the catalytic gasification of cellulose-derived biocarbons (CDC) with CO₂ using Fe as the catalyst. Fe(%wt)/CDC samples were synthesized through controlled pyrolysis of cellulose impregnated with iron precursors and evaluated under varying reaction temperatures and CO₂ concentrations. Characterization by XRD, TGA, Raman, TEM, and N₂ adsorption revealed that the initial Fe loading in cellulose not only determines the final carbon content in each Fe(%wt)/CDC sample but also plays a crucial role in regulating the textural and structural properties of the resulting carbonaceous materials, as well as the Fe nanoparticle size distribution. Specifically, higher Fe loading led to a decrease in surface area, reduction of microporosity, an increase of pore diameter, and to larger average Fe nanoparticle sizes. During gasification, Fe nanoparticles were oxidized by CO₂, resulting in a decline in catalytic activity and ultimately limiting the complete gasification of the carbonaceous material by the end of the reaction. These opposing effects explain the varying behaviour observed in the Fe(%wt)/CDC samples studied. Analysis of the initial gasification rates indicated that both, the apparent reaction order with respect to CO₂ and the activation energy, increased with reaction temperature and CO₂ partial pressure (p_CO₂), respectively. These results were successfully interpreted using a Langmuir-Hinshelwood model, which accounts for the influence of CO₂ adsorption on the observed reaction rate. These findings underscore the potential of Fe(%wt)/CDC materials for CO₂ utilization and biomass valorisation, providing valuable insights for the development of efficient catalytic gasification processes.

{"title":"Influence of operating conditions on the kinetics of Iron-catalysed gasification of biocarbons with CO2","authors":"D. Chaos-Hernández, N. Latorre, P. Tarifa, E. Romeo, A. Monzón","doi":"10.1016/j.cattod.2025.115289","DOIUrl":"10.1016/j.cattod.2025.115289","url":null,"abstract":"<div><div>In this study, we investigated the catalytic gasification of cellulose-derived biocarbons (CDC) with CO₂ using Fe as the catalyst. Fe(%wt)/CDC samples were synthesized through controlled pyrolysis of cellulose impregnated with iron precursors and evaluated under varying reaction temperatures and CO₂ concentrations. Characterization by XRD, TGA, Raman, TEM, and N₂ adsorption revealed that the initial Fe loading in cellulose not only determines the final carbon content in each Fe(%wt)/CDC sample but also plays a crucial role in regulating the textural and structural properties of the resulting carbonaceous materials, as well as the Fe nanoparticle size distribution. Specifically, higher Fe loading led to a decrease in surface area, reduction of microporosity, an increase of pore diameter, and to larger average Fe nanoparticle sizes. During gasification, Fe nanoparticles were oxidized by CO₂, resulting in a decline in catalytic activity and ultimately limiting the complete gasification of the carbonaceous material by the end of the reaction. These opposing effects explain the varying behaviour observed in the Fe(%wt)/CDC samples studied. Analysis of the initial gasification rates indicated that both, the apparent reaction order with respect to CO₂ and the activation energy, increased with reaction temperature and CO₂ partial pressure (p<sub>CO₂</sub>), respectively. These results were successfully interpreted using a Langmuir-Hinshelwood model, which accounts for the influence of CO₂ adsorption on the observed reaction rate. These findings underscore the potential of Fe(%wt)/CDC materials for CO₂ utilization and biomass valorisation, providing valuable insights for the development of efficient catalytic gasification processes.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115289"},"PeriodicalIF":5.2,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739808","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

Turning waste into value: Iron-cobalt bimetallic hydrochar for efficient removal of persistent chlorinated pollutants – Mechanistic insights and adsorption models

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-27 DOI: 10.1016/j.cattod.2025.115293

Himadri Rajput , Qian (Nancy) Lan , Rahil Changotra , Prachi Rajput , Pooja Devi , Yulin Hu , Quan (Sophia) He

In this study, a hydrothermal carbonization process was used to convert maple leaves into hydrochar, a sustainable bio-adsorbent, for the removal of pentachlorophenol (PCP) from wastewater. The hydrochar was further magnetized with iron and cobalt through hydrothermal treatment, enabling easy magnetic separation. Successful synthesis was confirmed by various physicochemical characterization techniques. Magnetic characteristics like saturation magnetization, remanence, and coercivity of synthesized hydrochar were studied to assess the functionalization. A removal efficiency of 94 % was achieved within 30 min at optimized conditions (0.06 g/L adsorbent dose, 10 mg/L initial PCP concentration, and pH 3). The adsorption process followed a pseudo-second-order kinetic model (R²= 0.995). Adsorption capacity decreased with an increasing pH from 3 to 11. At low pH values, the electrostatic interactions between PCP and adsorbent were favored by greater attractive forces. It was also observed that elevated temperature negatively impacted adsorption capacity. Reusability studies revealed a minimal reduction (16 %) in the removal efficiency over five cycles, highlighting the material’s durability. These findings demonstrated that the synthesized magnetic biosorbent effectively adsorbed PCP, and the adsorption capacity was influenced by factors like adsorbent dose, pH of reaction solution, and temperature.

{"title":"Turning waste into value: Iron-cobalt bimetallic hydrochar for efficient removal of persistent chlorinated pollutants – Mechanistic insights and adsorption models","authors":"Himadri Rajput , Qian (Nancy) Lan , Rahil Changotra , Prachi Rajput , Pooja Devi , Yulin Hu , Quan (Sophia) He","doi":"10.1016/j.cattod.2025.115293","DOIUrl":"10.1016/j.cattod.2025.115293","url":null,"abstract":"<div><div>In this study, a hydrothermal carbonization process was used to convert maple leaves into hydrochar, a sustainable bio-adsorbent, for the removal of pentachlorophenol (PCP) from wastewater. The hydrochar was further magnetized with iron and cobalt through hydrothermal treatment, enabling easy magnetic separation. Successful synthesis was confirmed by various physicochemical characterization techniques. Magnetic characteristics like saturation magnetization, remanence, and coercivity of synthesized hydrochar were studied to assess the functionalization. A removal efficiency of 94 % was achieved within 30 min at optimized conditions (0.06 g/L adsorbent dose, 10 mg/L initial PCP concentration, and pH 3). The adsorption process followed a pseudo-second-order kinetic model (R<sup>2</sup>= 0.995). Adsorption capacity decreased with an increasing pH from 3 to 11. At low pH values, the electrostatic interactions between PCP and adsorbent were favored by greater attractive forces. It was also observed that elevated temperature negatively impacted adsorption capacity. Reusability studies revealed a minimal reduction (16 %) in the removal efficiency over five cycles, highlighting the material’s durability. These findings demonstrated that the synthesized magnetic biosorbent effectively adsorbed PCP, and the adsorption capacity was influenced by factors like adsorbent dose, pH of reaction solution, and temperature.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115293"},"PeriodicalIF":5.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739806","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

B-doped GQD supported cobalt sulfide nanocomposite: A defect engineering approach for superior oxygen electrode performance

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-27 DOI: 10.1016/j.cattod.2025.115287

Uday Kumar Ghorui , MV R.Akshay Sampath , Gokul Sivaguru , Rituparna Dutta , Sambasivam Sangaraju , Sabyasachi Chakrabortty

Developing an efficient and durable electrocatalysts for oxygen electrolysis is crucial for advancing clean energy technologies. However, the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), along with catalyst degradation, remain major obstacles. Here, we optimized the composition of composite nanocatalysts obtained by doping of an electron deficient, B-atoms into graphene quantum dots (GQD) attached with Cobalt Sulfide (CoS) nanostructures. Optimizing the surface structure and investigating the interfacial interactions, the catalyst demonstrated an exceptional oxygen electrode reaction performance. The faster electronic synergism between the defect engineering BGQD and CoS offers more catalytic active sites as well as faster electrical conductivity and higher adsorption/desorption rate of oxygenated intermediates at the electrode surface for the electrolysis processes. Among the optimized composite electrode material CSBGQD-13 (CoS/BGQD (1:3)) exhibited high positive onset (E_onset = 1.04 V vs. RHE) and half-wave potential (E_1/2 = 0.84 V vs. RHE) with high limiting current density of 7.6 mA/cm² at 1600 rpm and a reasonable resistance to the MeOH crossover effect during ORR. In addition, our electrocatalyst demonstrated long-term durability and effective OER activity with the lowest Tafel slope of 82 mV/dec among other CSBGQDs and a lower overpotential of 0.27 V vs. RHE at a current density of 10 mA/cm². Furthermore, the CSBGQD-13 claims excellent dual function electrocatalytic performance towards ORR and OER with a very small ΔE value (only 0.66 V vs. RHE), a higher catalytic current density. Henceforth, for possible fuel cell applications, we believe that this electrode material may provide an understanding of the principles of metal sulfide carbon dots hybrid catalysts.

{"title":"B-doped GQD supported cobalt sulfide nanocomposite: A defect engineering approach for superior oxygen electrode performance","authors":"Uday Kumar Ghorui , MV R.Akshay Sampath , Gokul Sivaguru , Rituparna Dutta , Sambasivam Sangaraju , Sabyasachi Chakrabortty","doi":"10.1016/j.cattod.2025.115287","DOIUrl":"10.1016/j.cattod.2025.115287","url":null,"abstract":"<div><div>Developing an efficient and durable electrocatalysts for oxygen electrolysis is crucial for advancing clean energy technologies. However, the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), along with catalyst degradation, remain major obstacles. Here, we optimized the composition of composite nanocatalysts obtained by doping of an electron deficient, B-atoms into graphene quantum dots (GQD) attached with Cobalt Sulfide (CoS) nanostructures. Optimizing the surface structure and investigating the interfacial interactions, the catalyst demonstrated an exceptional oxygen electrode reaction performance. The faster electronic synergism between the defect engineering BGQD and CoS offers more catalytic active sites as well as faster electrical conductivity and higher adsorption/desorption rate of oxygenated intermediates at the electrode surface for the electrolysis processes. Among the optimized composite electrode material CSBGQD-13 (CoS/BGQD (1:3)) exhibited high positive onset (E<sub>onset</sub> = 1.04 V vs. RHE) and half-wave potential (E<sub>1/2</sub> = 0.84 V vs. RHE) with high limiting current density of 7.6 mA/cm<sup>2</sup> at 1600 rpm and a reasonable resistance to the MeOH crossover effect during ORR. In addition, our electrocatalyst demonstrated long-term durability and effective OER activity with the lowest Tafel slope of 82 mV/dec among other CSBGQDs and a lower overpotential of 0.27 V vs. RHE at a current density of 10 mA/cm<sup>2</sup>. Furthermore, the CSBGQD-13 claims excellent dual function electrocatalytic performance towards ORR and OER with a very small ΔE value (only 0.66 V vs. RHE), a higher catalytic current density. Henceforth, for possible fuel cell applications, we believe that this electrode material may provide an understanding of the principles of metal sulfide carbon dots hybrid catalysts.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115287"},"PeriodicalIF":5.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776565","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

Tailoring of single copper atoms anchored on N, P co-doped carbon for electrochemical CO2 reduction

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-26 DOI: 10.1016/j.cattod.2025.115284

David Ríos-Ruiz , Pablo Arévalo-Cid , Jesús Cebollada , Verónica Celorrio , María Victoria Martínez-Huerta

The electrochemical CO₂ reduction reaction (CO₂RR) is a promising strategy to convert the greenhouse gas CO₂ into valuable products using electricity as a feedstock. This study presents the development of single-atom copper catalyst anchored on a nitrogen and phosphorus co-doped carbon matrix designed for CO₂RR. The impact of carbonization temperature on the structural properties of the electrocatalysts, such as porosity and the electronic environment, was systematically examined, revealing its influence on the selectivity towards C₁ and C₂₊ products. Increased microporosity was associated with an enhanced hydrogen evolution reaction (HER), whereas mesoporosity contributed to improved CO₂ reduction reaction activity. Aberration-corrected transmission electron microscope evidenced that P addition improved the dispersion of Cu, whether in the form of single atoms or clusters. Moreover, phosphorus doping suppressed HER and promoted the formation of products such as methane, ethylene, and ethanol. The coexistence of Cu⁺, Cu⁰, and copper single atoms was identified as key to facilitating C-C bond formation. This study emphasizes the critical balance between textural and electronic properties in optimizing catalytic performance and provides valuable insights for designing advanced electrocatalysts for CO₂ valorization.

{"title":"Tailoring of single copper atoms anchored on N, P co-doped carbon for electrochemical CO2 reduction","authors":"David Ríos-Ruiz , Pablo Arévalo-Cid , Jesús Cebollada , Verónica Celorrio , María Victoria Martínez-Huerta","doi":"10.1016/j.cattod.2025.115284","DOIUrl":"10.1016/j.cattod.2025.115284","url":null,"abstract":"<div><div>The electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) is a promising strategy to convert the greenhouse gas CO<sub>2</sub> into valuable products using electricity as a feedstock. This study presents the development of single-atom copper catalyst anchored on a nitrogen and phosphorus co-doped carbon matrix designed for CO<sub>2</sub>RR. The impact of carbonization temperature on the structural properties of the electrocatalysts, such as porosity and the electronic environment, was systematically examined, revealing its influence on the selectivity towards C<sub>1</sub> and C<sub>2+</sub> products. Increased microporosity was associated with an enhanced hydrogen evolution reaction (HER), whereas mesoporosity contributed to improved CO<sub>2</sub> reduction reaction activity. Aberration-corrected transmission electron microscope evidenced that P addition improved the dispersion of Cu, whether in the form of single atoms or clusters. Moreover, phosphorus doping suppressed HER and promoted the formation of products such as methane, ethylene, and ethanol. The coexistence of Cu<sup>+</sup>, Cu<sup>0</sup>, and copper single atoms was identified as key to facilitating C-C bond formation. This study emphasizes the critical balance between textural and electronic properties in optimizing catalytic performance and provides valuable insights for designing advanced electrocatalysts for CO<sub>2</sub> valorization.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115284"},"PeriodicalIF":5.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725145","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

Comparative assessment of Mo/Ti and Mo/C catalysts for phenol hydrodeoxygenation: Influence of support and hydrogen treatment

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-24 DOI: 10.1016/j.cattod.2025.115291

Débora G.B. Dionizio , Priscilla M. de Souza , Cristiane A. Henriques , Gilles Berhault

Even if catalytic hydrodeoxygenation (HDO) is a promising approach for converting bio-oil into high-value products, this reaction process still faces challenges related to the inherent high hydrogen consumption needed to perform it. Therefore, the hydrodeoxygenation (HDO) of phenol was herein studied in the gas phase using molybdenum catalysts supported on titania (Mo/Ti) and activated carbon (Mo/C) at atmospheric pressure in order to evaluate the consequences of hydrogen treatment on the catalytic properties of these Mo-based HDO catalysts. Samples were characterized by ICP-OES, XRD, XPS, Raman, TPR, H₂O-TPD, and oxygen chemisorption, and the physicochemical properties were compared with their catalytic performances. Under the studied conditions, the support type and the hydrogen treatment cause changes in active species (MoO₂ and MoO₃), promoting different catalyst behaviors. However, all the catalysts studied were 100 % selective to benzene, indicating that the molybdenum active phase did not influence the selectivity of the reaction.

{"title":"Comparative assessment of Mo/Ti and Mo/C catalysts for phenol hydrodeoxygenation: Influence of support and hydrogen treatment","authors":"Débora G.B. Dionizio , Priscilla M. de Souza , Cristiane A. Henriques , Gilles Berhault","doi":"10.1016/j.cattod.2025.115291","DOIUrl":"10.1016/j.cattod.2025.115291","url":null,"abstract":"<div><div>Even if catalytic hydrodeoxygenation (HDO) is a promising approach for converting bio-oil into high-value products, this reaction process still faces challenges related to the inherent high hydrogen consumption needed to perform it. Therefore, the hydrodeoxygenation (HDO) of phenol was herein studied in the gas phase using molybdenum catalysts supported on titania (Mo/Ti) and activated carbon (Mo/C) at atmospheric pressure in order to evaluate the consequences of hydrogen treatment on the catalytic properties of these Mo-based HDO catalysts. Samples were characterized by ICP-OES, XRD, XPS, Raman, TPR, H<sub>2</sub>O-TPD, and oxygen chemisorption, and the physicochemical properties were compared with their catalytic performances. Under the studied conditions, the support type and the hydrogen treatment cause changes in active species (MoO<sub>2</sub> and MoO<sub>3</sub>), promoting different catalyst behaviors. However, all the catalysts studied were 100 % selective to benzene, indicating that the molybdenum active phase did not influence the selectivity of the reaction.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115291"},"PeriodicalIF":5.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143735333","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

Chemo-enzymatic phenol polymerisation via in-situ H2O2 synthesis

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-24 DOI: 10.1016/j.cattod.2025.115292

Liwei Zhang , Richard J. Lewis , Joseph Brehm , Wencong Liu , David J. Morgan , Thomas E. Davies , Yong Wang , Graham J. Hutchings

Within this contribution, the combination of supported AuPd nanoalloys with horseradish peroxidase is demonstrated to offer high efficacy towards the one-pot oxidative polymerisation of the model wastewater contaminant phenol, via the chemo-catalytic supply of in-situ generated H₂O₂_. Notably, the utilisation of AuPd alloyed formulations offered considerably improved cascade efficiencies, compared to that observed over monometallic analogues, with the optimal 0.5%Au-0.5%Pd/TiO₂ catalyst achieving total conversion of phenol within 15 minutes when used in conjunction with the enzyme. Importantly, the in-situ chemo-enzymatic system was shown to offer good stability over successive reactions, and outperforms analogous approaches reliant on the use of preformed H₂O₂, while also avoiding the proprietary stabilising agents present in the commercial oxidant.

引用次数: 0

Catalytic behavior of ITQ-13 zeolite in benzene and toluene ethylation

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-22 DOI: 10.1016/j.cattod.2025.115288

M. Teresa Portilla , Avelino Corma , Cristina Martínez , Susana Valencia , Francisco J. Llopis

The ITQ-13 zeolite (ITH) presents a three-dimensional channel system formed by channels delimited by rings of 9 and 10 tetrahedra (9MR and 10MR). This material has been studied as a catalyst in reactions of interest in the petrochemical industry, which are carried out on a commercial scale in the presence of medium-pore zeolites, such as the alkylation of benzene or toluene with ethylene or ethanol. Due to its acidic properties and its particular topology, zeolite ITQ-13 presents a comparable activity to that of ZSM-5 or MCM-22, employed at commercial scale, but also higher selectivity to the main alkylation products and lower deactivation rate. The large cavities located at the intersections between the 9MR and 10MR channels, capable of hosting larger reaction intermediates than ZSM-5, and the greater activity of its external surface, could be responsible for the improved catalytic behavior of ITQ-13.

引用次数: 0

Performance of Ni-M/Ca12Al14O33 (M= Co, Cu and Fe) bimetallic catalysts in sorption-enhanced steam methane reforming for blue hydrogen production Ni-M/Ca12Al14O33（M= Co、Cu 和 Fe）双金属催化剂在吸附强化蒸汽甲烷转化制取蓝色氢气中的性能

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-22 DOI: 10.1016/j.cattod.2025.115281

Ahmad Salam Farooqi , Muhammad Zubair Shahid , Mohamed Essalhi , Mohammad M. Hossain , Mahmoud M. Abdelnaby , Mohammed A. Sanhoob , Vasilije Manovic , Medhat A. Nemitallah

The sorption-enhanced steam methane reforming (SE-SMR) represents a significant advancement in clean hydrogen production. By integrating methane steam reforming with in-situ CO₂ capture, this process offers a sustainable method for hydrogen production while minimizing CO₂ emissions. This study investigates the catalytic performance of monometallic Ni/Ca₁₂Al₁₄O₃₃ and three bimetallic catalysts (Ni-M/Ca₁₂Al₁₄O₃₃, where M=Co, Cu, and Fe) for the SE-SMR reaction. The materials were synthesized using a wet impregnation method and characterized through XRD, XRF, BET, SEM, and TGA to assess their structural, textural, and CO₂ sorption properties. The SE-SMR reaction was conducted in a fixed bed reactor at 700 ℃ with a steam-to-carbon (S/C) ratio of 3, focusing on evaluating catalyst activity, stability, and he synergistic effects of catalytic reforming and CO₂ sorption capacity. The XRD analysis of fresh samples revealed the presence of free CaO, which aids in capturing CO₂ during the reaction. The Ni/Ca₁₂Al₁₄O₃₃ catalyst displayed promising initial activity, which gradually decreased due to sorbent saturation. Among the bimetallic catalysts, Ni-Co/Ca₁₂Al₁₄O₃₃ exhibited the highest average hydrogen purity (78 %) and superior stability due to the synergistic effect of Co and Ni. The Ni-Cu catalyst demonstrated moderate hydrogen purity (∼50 %), whereas the Ni-Fe catalyst showed relatively poor performance, likely due to unfavourable interactions between Ni and Fe, as indicated by XRD. Additionally, the TGA results revealed that Ni-Co/Ca₁₂Al₁₄O₃₃ also maintained excellent cyclic stability for CO₂ adsorption and regeneration over 10 cycles. The kinetic parameters of CO₂ adsorption were estimated using a double exponential method, which indicated the highest specific sorption rate constant for the Ni-Co/Ca₁₂Al₁₄O₃₃ sample.

{"title":"Performance of Ni-M/Ca12Al14O33 (M= Co, Cu and Fe) bimetallic catalysts in sorption-enhanced steam methane reforming for blue hydrogen production","authors":"Ahmad Salam Farooqi , Muhammad Zubair Shahid , Mohamed Essalhi , Mohammad M. Hossain , Mahmoud M. Abdelnaby , Mohammed A. Sanhoob , Vasilije Manovic , Medhat A. Nemitallah","doi":"10.1016/j.cattod.2025.115281","DOIUrl":"10.1016/j.cattod.2025.115281","url":null,"abstract":"<div><div>The sorption-enhanced steam methane reforming (SE-SMR) represents a significant advancement in clean hydrogen production. By integrating methane steam reforming with in-situ CO<sub>2</sub> capture, this process offers a sustainable method for hydrogen production while minimizing CO<sub>2</sub> emissions. This study investigates the catalytic performance of monometallic Ni/Ca<sub>12</sub>Al<sub>14</sub>O<sub>33</sub> and three bimetallic catalysts (Ni-M/Ca<sub>12</sub>Al<sub>14</sub>O<sub>33</sub>, where M=Co, Cu, and Fe) for the SE-SMR reaction. The materials were synthesized using a wet impregnation method and characterized through XRD, XRF, BET, SEM, and TGA to assess their structural, textural, and CO<sub>2</sub> sorption properties. The SE-SMR reaction was conducted in a fixed bed reactor at 700 ℃ with a steam-to-carbon (S/C) ratio of 3, focusing on evaluating catalyst activity, stability, and he synergistic effects of catalytic reforming and CO<sub>2</sub> sorption capacity. The XRD analysis of fresh samples revealed the presence of free CaO, which aids in capturing CO<sub>2</sub> during the reaction. The Ni/Ca₁₂Al₁₄O₃₃ catalyst displayed promising initial activity, which gradually decreased due to sorbent saturation. Among the bimetallic catalysts, Ni-Co/Ca₁₂Al₁₄O₃₃ exhibited the highest average hydrogen purity (78 %) and superior stability due to the synergistic effect of Co and Ni. The Ni-Cu catalyst demonstrated moderate hydrogen purity (∼50 %), whereas the Ni-Fe catalyst showed relatively poor performance, likely due to unfavourable interactions between Ni and Fe, as indicated by XRD. Additionally, the TGA results revealed that Ni-Co/Ca<sub>12</sub>Al<sub>14</sub>O<sub>33</sub> also maintained excellent cyclic stability for CO<sub>2</sub> adsorption and regeneration over 10 cycles. The kinetic parameters of CO<sub>2</sub> adsorption were estimated using a double exponential method, which indicated the highest specific sorption rate constant for the Ni-Co/Ca<sub>12</sub>Al<sub>14</sub>O<sub>33</sub> sample.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115281"},"PeriodicalIF":5.2,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705045","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

Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-20 DOI: 10.1016/j.cattod.2025.115283

Aitor Arandia , Jorge A. Velasco , Ahmed Sajid , Jihong Yim , Hammad Shamshad , Hua Jiang , Ashish Chahal , Abhinash Kumar Singh , Christine Gonsalves , Reetta Karinen , Riikka L. Puurunen

Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.

{"title":"Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support","authors":"Aitor Arandia , Jorge A. Velasco , Ahmed Sajid , Jihong Yim , Hammad Shamshad , Hua Jiang , Ashish Chahal , Abhinash Kumar Singh , Christine Gonsalves , Reetta Karinen , Riikka L. Puurunen","doi":"10.1016/j.cattod.2025.115283","DOIUrl":"10.1016/j.cattod.2025.115283","url":null,"abstract":"<div><div>Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115283"},"PeriodicalIF":5.2,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697760","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}

引用次数: 0

CO2 facilitated aromatization of butenes to benzene, toluene and xylene

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-03-19 DOI: 10.1016/j.cattod.2025.115285

Yu Shao , Yi Ding , Feng Jiao , Dengyun Miao , Shujing Guo , Junfeng Wang , Xiulian Pan

The aromatization of mixed C₄ olefins is an important way to convert low value industrial C₄ hydrocarbons by-products into value-added chemicals. Herein, we report CO₂ facilitated aromatization of C₄ olefins to benzene, toluene and xylene (BTX) using metal oxide-zeolite (OXZEO) bifunctional catalysts. An aromatics selectivity of 80.0 % at a CO₂ conversion 10.5 % and butene conversion ∼100 % has been obtained at 500 °C and 1.0 MPa. The proportion of BTX in aromatics reaches as high as 91.0 %. Detailed characterization reveals that the Brønsted acid sites of ZSM-5 are the active sites for aromatization, while the presence of ZnCrAlO_x oxides provides adsorption sites for CO₂ and further reaction with the hydrogen species generated during aromatization. The presence of CO₂ not only enhances the selectivity of aromatics, but also improves the stability of the reaction. ¹³C isotope experiments demonstrate that CO₂ participates in the formation of aromatics. Furthermore, this new strategy is applicable for utilization of different sources of mixed C₄ olefins and C₄-C₅ olefins, in addition to the benefits of utilizing CO₂ towards a sustainable decarbonized society.

{"title":"CO2 facilitated aromatization of butenes to benzene, toluene and xylene","authors":"Yu Shao , Yi Ding , Feng Jiao , Dengyun Miao , Shujing Guo , Junfeng Wang , Xiulian Pan","doi":"10.1016/j.cattod.2025.115285","DOIUrl":"10.1016/j.cattod.2025.115285","url":null,"abstract":"<div><div>The aromatization of mixed C<sub>4</sub> olefins is an important way to convert low value industrial C<sub>4</sub> hydrocarbons by-products into value-added chemicals. Herein, we report CO<sub>2</sub> facilitated aromatization of C<sub>4</sub> olefins to benzene, toluene and xylene (BTX) using metal oxide-zeolite (OXZEO) bifunctional catalysts. An aromatics selectivity of 80.0 % at a CO<sub>2</sub> conversion 10.5 % and butene conversion ∼100 % has been obtained at 500 °C and 1.0 MPa. The proportion of BTX in aromatics reaches as high as 91.0 %. Detailed characterization reveals that the Brønsted acid sites of ZSM-5 are the active sites for aromatization, while the presence of ZnCrAlO<sub>x</sub> oxides provides adsorption sites for CO<sub>2</sub> and further reaction with the hydrogen species generated during aromatization. The presence of CO<sub>2</sub> not only enhances the selectivity of aromatics, but also improves the stability of the reaction. <sup>13</sup>C isotope experiments demonstrate that CO<sub>2</sub> participates in the formation of aromatics. Furthermore, this new strategy is applicable for utilization of different sources of mixed C<sub>4</sub> olefins and C<sub>4</sub>-C<sub>5</sub> olefins, in addition to the benefits of utilizing CO<sub>2</sub> towards a sustainable decarbonized society.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"454 ","pages":"Article 115285"},"PeriodicalIF":5.2,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739807","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

首页上一页

下一页尾页

类型

全部化学•材料生命科学医学物理工程技术环境•农林材料科学地球科学法学管理学化学环境科学与生态学计算机科学教育学经济学农林科学人文科学生物学数学物理与天体物理心理学综合性期刊其他工业工程理学历史学农学文学信息工程

数据库

全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Catalysis Today

全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.

﹀