Pub Date : 2025-12-27DOI: 10.1016/j.cattod.2025.115672
Pengfei Guo , Jinfei Lu , Meng Liu , Nanfang Tang , Zhijie Wu , Lu Lin , Wenhao Luo
The reductive amination of furfural (FUR) to furfurylamine (FAM) is one of the key reactions for the sustainable production of value-added primary amines in biomass valorization. Herein, we have constructed a series of N-doped porous carbon confined Co nanoparticles (CoNC) based on the pyrolysis of Co-containing ZIF-67 at different temperatures for the synthesis of FAM from FUR. The reductive amination activity of as-obtained CoNC catalysts shows a volcano plot as the pyrolysis temperature increases. The optimal CoNC-750, obtained by pyrolysis at 750 ℃, could afford a maximum FAM yield up to 99 % at 110 ℃, 0.3 MPa of NH3, 2 MPa of H2 in methanol, reflecting one of the excellent performances in terms of FAM yields for Co-based catalysts. Besides, no apparent deactivation of the CoNC-750 is observed after six consecutive runs, indicating an excellent stability. Through a combination of advanced characterizations, a positive linear relationship between the densities of the strong acid sites and the corresponding FAM productivities of CoNC catalysts has been revealed, indicating that the strong acid density is a key descriptor for facilitating the FUR-to-FAM transformation. This study provides an efficient approach for fabricating high-performing non-noble metal catalysts for the reductive amination of biomass-derived platform molecules, which could be of great aid for green and sustainable production of primary amines and beyond.
{"title":"ZIF-67-derived confined cobalt catalysts for reductive amination of furfural to furfurylamine","authors":"Pengfei Guo , Jinfei Lu , Meng Liu , Nanfang Tang , Zhijie Wu , Lu Lin , Wenhao Luo","doi":"10.1016/j.cattod.2025.115672","DOIUrl":"10.1016/j.cattod.2025.115672","url":null,"abstract":"<div><div>The reductive amination of furfural (FUR) to furfurylamine (FAM) is one of the key reactions for the sustainable production of value-added primary amines in biomass valorization. Herein, we have constructed a series of N-doped porous carbon confined Co nanoparticles (CoNC) based on the pyrolysis of Co-containing ZIF-67 at different temperatures for the synthesis of FAM from FUR. The reductive amination activity of as-obtained CoNC catalysts shows a volcano plot as the pyrolysis temperature increases. The optimal CoNC-750, obtained by pyrolysis at 750 ℃, could afford a maximum FAM yield up to 99 % at 110 ℃, 0.3 MPa of NH<sub>3</sub>, 2 MPa of H<sub>2</sub> in methanol, reflecting one of the excellent performances in terms of FAM yields for Co-based catalysts. Besides, no apparent deactivation of the CoNC-750 is observed after six consecutive runs, indicating an excellent stability. Through a combination of advanced characterizations, a positive linear relationship between the densities of the strong acid sites and the corresponding FAM productivities of CoNC catalysts has been revealed, indicating that the strong acid density is a key descriptor for facilitating the FUR-to-FAM transformation. This study provides an efficient approach for fabricating high-performing non-noble metal catalysts for the reductive amination of biomass-derived platform molecules, which could be of great aid for green and sustainable production of primary amines and beyond.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115672"},"PeriodicalIF":5.3,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882180","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}
Pub Date : 2025-12-24DOI: 10.1016/j.cattod.2025.115674
Maryam Ahmadi , Seyed Mehdi Alavi , Ali Akbar Asgharinezhad , Azadeh Haghighatzadeh , Afsanehsadat Larimi
This study investigates the photocatalytic reduction of CO2 using water vapor in a top-irradiation batch reactor, with M-Bi2MoO6/TiO2 serving as the photocatalyst. Various M-Bi2MoO6/TiO2 samples with different co-catalysts (M: Ni, Ce, Co, Mo, Cu) were fabricated through a deposition-ultrasound-assisted approach. The prepared samples underwent examination using UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), X-ray diffraction (XRD), Field-emission scanning electron microscopy (FESEM), N2 adsorption-desorption isotherms, Photoluminescence (PL) and Raman spectroscopy. Methane was identified as the predominant reaction product, and the introduction of co-catalysts through sono-deposition significantly improved the photocatalytic efficiency. The catalysts with various co-catalysts showed different performances in CO2 reduction. Additionally, the optical properties of the composite samples changed with the deposition of different co-catalysts on the BT support. Compared to pristine TiO2, the co-catalyst-loaded composites exhibited superior CO2 reduction performance. Among them, the Ni-BT sample had the highest methane yield, attributed to the even distribution of Ni nanoparticles, better visible-light absorption, and more effective charge separation and transfer.
{"title":"Uniform sono-dispersed co-catalysts unlock superior CO₂ photoreduction on Bi₂MoO₆/TiO₂","authors":"Maryam Ahmadi , Seyed Mehdi Alavi , Ali Akbar Asgharinezhad , Azadeh Haghighatzadeh , Afsanehsadat Larimi","doi":"10.1016/j.cattod.2025.115674","DOIUrl":"10.1016/j.cattod.2025.115674","url":null,"abstract":"<div><div>This study investigates the photocatalytic reduction of CO<sub>2</sub> using water vapor in a top-irradiation batch reactor, with M-Bi<sub>2</sub>MoO<sub>6</sub>/TiO<sub>2</sub> serving as the photocatalyst. Various M-Bi<sub>2</sub>MoO<sub>6</sub>/TiO<sub>2</sub> samples with different co-catalysts (M: Ni, Ce, Co, Mo, Cu) were fabricated through a deposition-ultrasound-assisted approach. The prepared samples underwent examination using UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), X-ray diffraction (XRD), Field-emission scanning electron microscopy (FESEM), N<sub>2</sub> adsorption-desorption isotherms, Photoluminescence (PL) and Raman spectroscopy. Methane was identified as the predominant reaction product, and the introduction of co-catalysts through sono-deposition significantly improved the photocatalytic efficiency. The catalysts with various co-catalysts showed different performances in CO<sub>2</sub> reduction. Additionally, the optical properties of the composite samples changed with the deposition of different co-catalysts on the BT support. Compared to pristine TiO<sub>2</sub>, the co-catalyst-loaded composites exhibited superior CO<sub>2</sub> reduction performance. Among them, the Ni-BT sample had the highest methane yield, attributed to the even distribution of Ni nanoparticles, better visible-light absorption, and more effective charge separation and transfer.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115674"},"PeriodicalIF":5.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882181","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}
Catalytic oxidation of toluene represents a promising strategy for the treatment of industrial exhaust gases. Synthesizing efficient catalysts derived from solid waste for toluene removal holds great application potential, but remains challenging due to the low density of active sites, poor mass transfer, and structural instability. This study proposed a “defect-directed conversion and Ca-Fe electronic synergy” strategy to fabricate Fe-Ca composite catalysts using magnetic iron oxide waste and industrial lime for the catalytic oxidation of toluene. Ball milling for 2 h activated hydroxyl defects on iron slag, enabling metastable Ca2Fe2O5 formation at a CaO/Fe2O3 molar ratio of 1:1.5, which enhanced toluene diffusion and activation. Compared to Fe2O3, the Ca1Fe1.5 catalyst exhibits a 50℃ reduction in the temperature required for complete toluene conversion and excellent selectivity toward carbon dioxide. XRD/EPR confirm Ca2Fe2O5 in Ca1Fe1.5 transforms to CaO/α-Fe with high-density oxygen vacancies under reaction conditions. DFT further reveals Ca2Fe2O5 (1.28 eV) has lower oxygen vacancy formation energy than Fe2O3 (2.4 eV), boosting lattice oxygen migration. O2-TPD/H2-TPR manifest that the oxygen vacancy concentration in Ca1Fe1.5 is 2.3 times higher than that in Fe2O3, boosting lattice oxygen migration and redox cycle. XPS demonstrates Fe-O-Ca interfacial charge redistribution raises Fe3 + /(Fe3++Fe2+) from 1.32 to 1.99, lowering oxygen radical activation energy and promoting active oxygen (O-/O2-) generation. Furthermore, the larger absolute value of the toluene adsorption energy on Ca2Fe2O5 (-0.31 eV) than on Fe2O3 (-0.078 eV) suggests that the Fe-Ca interaction, facilitating subsequent reaction pathways and improving CO2 yield. In situ DRIFTS shows the formation of more reactive intermediates over Ca1Fe1.5, thus accelerating toluene degradation. The mechanism of oxygen vacancy regeneration drives the efficient oxidation of toluene at low temperatures.
{"title":"Enhancing toluene oxidation performance of Fe2O3–CaO catalysts through the formation of oxygen-vacancy-rich Ca2Fe2O5","authors":"Qianyu Tao, Yuxue Zhu, Xiaokun Yi, Jiahui Wei, Wenjun Liang, Running Kang","doi":"10.1016/j.cattod.2025.115675","DOIUrl":"10.1016/j.cattod.2025.115675","url":null,"abstract":"<div><div>Catalytic oxidation of toluene represents a promising strategy for the treatment of industrial exhaust gases. Synthesizing efficient catalysts derived from solid waste for toluene removal holds great application potential, but remains challenging due to the low density of active sites, poor mass transfer, and structural instability. This study proposed a “defect-directed conversion and Ca-Fe electronic synergy” strategy to fabricate Fe-Ca composite catalysts using magnetic iron oxide waste and industrial lime for the catalytic oxidation of toluene. Ball milling for 2 h activated hydroxyl defects on iron slag, enabling metastable Ca<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> formation at a CaO/Fe<sub>2</sub>O<sub>3</sub> molar ratio of 1:1.5, which enhanced toluene diffusion and activation. Compared to Fe<sub>2</sub>O<sub>3</sub>, the Ca<sub>1</sub>Fe<sub>1.5</sub> catalyst exhibits a 50℃ reduction in the temperature required for complete toluene conversion and excellent selectivity toward carbon dioxide. XRD/EPR confirm Ca<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> in Ca<sub>1</sub>Fe<sub>1.5</sub> transforms to CaO/α-Fe with high-density oxygen vacancies under reaction conditions. DFT further reveals Ca<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> (1.28 eV) has lower oxygen vacancy formation energy than Fe<sub>2</sub>O<sub>3</sub> (2.4 eV), boosting lattice oxygen migration. O<sub>2</sub>-TPD/H<sub>2</sub>-TPR manifest that the oxygen vacancy concentration in Ca<sub>1</sub>Fe<sub>1.5</sub> is 2.3 times higher than that in Fe<sub>2</sub>O<sub>3</sub>, boosting lattice oxygen migration and redox cycle. XPS demonstrates Fe-O-Ca interfacial charge redistribution raises Fe<sup>3 +</sup> /(Fe<sup>3+</sup>+Fe<sup>2+</sup>) from 1.32 to 1.99, lowering oxygen radical activation energy and promoting active oxygen (O<sup>-</sup>/O<sub>2</sub><sup>-</sup>) generation. Furthermore, the larger absolute value of the toluene adsorption energy on Ca<sub>2</sub>Fe<sub>2</sub>O<sub>5</sub> (-0.31 eV) than on Fe<sub>2</sub>O<sub>3</sub> (-0.078 eV) suggests that the Fe-Ca interaction, facilitating subsequent reaction pathways and improving CO<sub>2</sub> yield. <em>In situ</em> DRIFTS shows the formation of more reactive intermediates over Ca<sub>1</sub>Fe<sub>1.5</sub>, thus accelerating toluene degradation. The mechanism of oxygen vacancy regeneration drives the efficient oxidation of toluene at low temperatures.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115675"},"PeriodicalIF":5.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882182","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}
Pub Date : 2025-12-23DOI: 10.1016/j.cattod.2025.115671
Rui Feng , Wei Wang , Junchao Luo , Tianbo Li , Xiaoyan Hu , Xinlong Yan , Shijian Lu
This study presents a comparative investigation of hierarchical and nanosized SAPO-34 catalysts for methanol-to-olefins (MTO) conversion. Hierarchical SAPO-34 (SP-Hx) was synthesized using PEG-4000 as a mesopore template, while nanosized SAPO-34 (SP-Nx) was prepared via a seed-assisted method. Characterization revealed that SP-H2 exhibited a hierarchical pore structure with enhanced external surface area (84 m2·g−1) and mesopore volume (0.35 cm3·g−1), whereas SP-N3 demonstrated reduced crystallite size of approximately 700 nm and higher acid site density. Catalytic tests showed that SP-N3 achieved the longest lifetime (625 min), a 2.2-fold increase over conventional SP-0 (275 min), attributed to its optimized acidity and shortened diffusion pathways. Hierarchical SP-H2 also exhibited improved stability (365 min) due to increased coke storage capacity. Coke analysis indicated that pore blockage by polycyclic aromatic hydrocarbons (PAHs) was the primary deactivation mechanism. These findings highlight the potential of nano-structuring and hierarchical design to enhance MTO catalyst performance.
{"title":"Comparative study of hierarchical and nanosized SAPO-34 catalysts in methanol to olefins","authors":"Rui Feng , Wei Wang , Junchao Luo , Tianbo Li , Xiaoyan Hu , Xinlong Yan , Shijian Lu","doi":"10.1016/j.cattod.2025.115671","DOIUrl":"10.1016/j.cattod.2025.115671","url":null,"abstract":"<div><div>This study presents a comparative investigation of hierarchical and nanosized SAPO-34 catalysts for methanol-to-olefins (MTO) conversion. Hierarchical SAPO-34 (SP-H<em>x</em>) was synthesized using PEG-4000 as a mesopore template, while nanosized SAPO-34 (SP-N<em>x</em>) was prepared via a seed-assisted method. Characterization revealed that SP-H2 exhibited a hierarchical pore structure with enhanced external surface area (84 m<sup>2</sup>·g<sup>−1</sup>) and mesopore volume (0.35 cm<sup>3</sup>·g<sup>−1</sup>), whereas SP-N3 demonstrated reduced crystallite size of approximately 700 nm and higher acid site density. Catalytic tests showed that SP-N3 achieved the longest lifetime (625 min), a 2.2-fold increase over conventional SP-0 (275 min), attributed to its optimized acidity and shortened diffusion pathways. Hierarchical SP-H2 also exhibited improved stability (365 min) due to increased coke storage capacity. Coke analysis indicated that pore blockage by polycyclic aromatic hydrocarbons (PAHs) was the primary deactivation mechanism. These findings highlight the potential of nano-structuring and hierarchical design to enhance MTO catalyst performance.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115671"},"PeriodicalIF":5.3,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838675","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}
Pub Date : 2025-12-23DOI: 10.1016/j.cattod.2025.115668
Eun Ji Kim , Dong Chan Park , Sang Hun Choi , Sein Hwang , Do Heui Kim , Inhak Song
The influence of alkali metal precursor on Dual-Function Materials (DFMs) for integrated CO2 capture and methanation has not been thoroughly explored. This study systematically investigated the effect of sodium carbonate and sodium nitrate precursors on Na-Ru/Al2O3 DFM performance. The two precursors exhibited markedly different thermal decomposition behaviors. After calcination at 400 °C, carbonate precursors retained 3.7 % carbon while nitrate precursors underwent complete decomposition. This difference proved critical for catalyst performance. Catalysts derived from sodium carbonate precursors (Na(C)-Ru/Al) produced 1.9 times less methane than the sodium nitrate-derived catalysts (Na(N)-Ru/Al). They also showed delayed methane formation with substantial CO2 detected upon hydrogen injection for methanation. Even after substantial decomposition of carbonate precursor at 600 °C it exhibited low activity. Initial methane formation rates of Na(C)-Ru/Al600 sample reached only 0.56 μmol/min·gcat compared to 1.52 μmol/min·gcat for the nitrate-based system, Na(N)-Ru/Al600. XRD analysis revealed progressive sodium aluminate formation upon carbonate decomposition, which likely contributed to the low methane productivity by hindering RuOx reduction. This structural transformation elevated RuOx reduction temperature from 148 °C (Ru/Al400_600 reference) to 223 °C. In contrast, nitrate-derived samples prevented this structural change and maintained optimal reduction of RuOx at 124 °C. The impact of calcination atmosphere on catalyst stability was also investigated by calcining Na(C)-Ru/Al samples under static air, CO2, O2, and N2 atmospheres. Notably, calcination under CO2 atmosphere prevented Ru volatilization and maintained optimal Na+ dispersion. In contrast, other atmospheres led to detrimental NaAlO2 formation, which is associated with catalytic performance.
{"title":"Effect of sodium precursors on Na-Ru/Al2O3 dual function materials for integrated CO2 capture and methanation","authors":"Eun Ji Kim , Dong Chan Park , Sang Hun Choi , Sein Hwang , Do Heui Kim , Inhak Song","doi":"10.1016/j.cattod.2025.115668","DOIUrl":"10.1016/j.cattod.2025.115668","url":null,"abstract":"<div><div>The influence of alkali metal precursor on Dual-Function Materials (DFMs) for integrated CO<sub>2</sub> capture and methanation has not been thoroughly explored. This study systematically investigated the effect of sodium carbonate and sodium nitrate precursors on Na-Ru/Al<sub>2</sub>O<sub>3</sub> DFM performance. The two precursors exhibited markedly different thermal decomposition behaviors. After calcination at 400 °C, carbonate precursors retained 3.7 % carbon while nitrate precursors underwent complete decomposition. This difference proved critical for catalyst performance. Catalysts derived from sodium carbonate precursors (Na(C)-Ru/Al) produced 1.9 times less methane than the sodium nitrate-derived catalysts (Na(N)-Ru/Al). They also showed delayed methane formation with substantial CO<sub>2</sub> detected upon hydrogen injection for methanation. Even after substantial decomposition of carbonate precursor at 600 °C it exhibited low activity. Initial methane formation rates of Na(C)-Ru/Al600 sample reached only 0.56 μmol/min·g<sub>cat</sub> compared to 1.52 μmol/min·g<sub>cat</sub> for the nitrate-based system, Na(N)-Ru/Al600. XRD analysis revealed progressive sodium aluminate formation upon carbonate decomposition, which likely contributed to the low methane productivity by hindering RuO<sub>x</sub> reduction. This structural transformation elevated RuO<sub>x</sub> reduction temperature from 148 °C (Ru/Al400_600 reference) to 223 °C. In contrast, nitrate-derived samples prevented this structural change and maintained optimal reduction of RuO<sub>x</sub> at 124 °C. The impact of calcination atmosphere on catalyst stability was also investigated by calcining Na(C)-Ru/Al samples under static air, CO<sub>2</sub>, O<sub>2</sub>, and N<sub>2</sub> atmospheres. Notably, calcination under CO<sub>2</sub> atmosphere prevented Ru volatilization and maintained optimal Na<sup>+</sup> dispersion. In contrast, other atmospheres led to detrimental NaAlO<sub>2</sub> formation, which is associated with catalytic performance.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115668"},"PeriodicalIF":5.3,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838676","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}
A promising route for the valorization of acid gas (CO₂ and H₂S) components involves their simultaneous transformation into carbon monoxide and sulfur, through carbonyl sulfide (COS) intermediate. In this work, we systematically explore the catalytic performance of 13X and 4 A for COS formation under varying conditions of temperature, acid gas partial pressure, and zeolite hydration state. H2S, CO2, and COS breakthrough experiments at 45 °C reveal that the capacities of all three molecules are higher for 13X than for 4 A. Thermal gravimetry on hydrated zeolites specifies water contents of 13.1 and 12.0 mmol/g for 13X and 4 A, respectively. COS yield is highest at 100 °C, showing temperature dependence in the case of 13X; in contrast, 4 A retains more than 70 % of its maximum activity over an extended range of temperatures. An increase in acid gas partial pressure from 0.2 to 0.8 bar gradually increases the total COS in 13X, whereas the activity of 4 A remains constant. Likewise, COS formation increases with decreasing zeolite hydration; threshold-dependent in 13X but progressive and relatively less pronounced in 4 A. Both zeolites, independent of conditions, undergo a decline in COS formation over time due to the water-induced inhibition of active sites, attributed to poisoning. While activity in 4 A decays rapidly, 13X exhibits a more gradual decay, corresponding to the inhibitory effect of the produced water being less pronounced in 13X than in 4 A. This reduces competitive adsorption on active sites and mitigates site blockage in 13X, which in turn preserves catalytic performance over time, indicating that 13X is more sensitive to changing conditions than 4 A. An optimum operating window identified for the two materials can help reduce the energy required for the industrial conversion of acid gas and subsequent catalyst regeneration. This corresponds to reaction at 120 °C and 250 °C and the regeneration at 250 °C and 300 °C for 13X and 4 A, respectively.
{"title":"Acid gas valorization through a carbonyl sulfide (COS) intermediate over Na-containing FAU and LTA zeolites","authors":"Syeda Rabia Batool , Marco Fabbiani , Alexey Novikov , Raman Ghassemi , Soroush Zareghorbaei , Jeroen Lauwaert , Ludovic Pinard , Helene Retot , Joris W. Thybaut , Valentin Valtchev","doi":"10.1016/j.cattod.2025.115660","DOIUrl":"10.1016/j.cattod.2025.115660","url":null,"abstract":"<div><div>A promising route for the valorization of acid gas (CO₂ and H₂S) components involves their simultaneous transformation into carbon monoxide and sulfur, through carbonyl sulfide (COS) intermediate. In this work, we systematically explore the catalytic performance of 13X and 4 A for COS formation under varying conditions of temperature, acid gas partial pressure, and zeolite hydration state. H<sub>2</sub>S, CO<sub>2</sub>, and COS breakthrough experiments at 45 °C reveal that the capacities of all three molecules are higher for 13X than for 4 A. Thermal gravimetry on hydrated zeolites specifies water contents of 13.1 and 12.0 mmol/g for 13X and 4 A, respectively. COS yield is highest at 100 °C, showing temperature dependence in the case of 13X; in contrast, 4 A retains more than 70 % of its maximum activity over an extended range of temperatures. An increase in acid gas partial pressure from 0.2 to 0.8 bar gradually increases the total COS in 13X, whereas the activity of 4 A remains constant. Likewise, COS formation increases with decreasing zeolite hydration; threshold-dependent in 13X but progressive and relatively less pronounced in 4 A. Both zeolites, independent of conditions, undergo a decline in COS formation over time due to the water-induced inhibition of active sites, attributed to poisoning. While activity in 4 A decays rapidly, 13X exhibits a more gradual decay, corresponding to the inhibitory effect of the produced water being less pronounced in 13X than in 4 A. This reduces competitive adsorption on active sites and mitigates site blockage in 13X, which in turn preserves catalytic performance over time, indicating that 13X is more sensitive to changing conditions than 4 A. An optimum operating window identified for the two materials can help reduce the energy required for the industrial conversion of acid gas and subsequent catalyst regeneration. This corresponds to reaction at 120 °C and 250 °C and the regeneration at 250 °C and 300 °C for 13X and 4 A, respectively.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115660"},"PeriodicalIF":5.3,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882179","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}
Pub Date : 2025-12-21DOI: 10.1016/j.cattod.2025.115661
Yupeng Tian , Yujia Liu , Shoutao Ma , Wei Xu , Chenyang Zhao , Bing Sun
This study introduces a heart-like micromixer reactor and Au/TS-1 catalyst to address the dual challenges of safety and efficiency in gas-phase propylene epoxidation using H2 and O2. Conventional methods face inherent explosion risks and rapid catalyst deactivation due to sintering and coking. The microreactor architecture achieves over 99 % flame-quenching efficiency via sub-millisecond radical suppression and enhanced heat transfer, enabling safe operation with minimal inert gas dilution (N2 < 70 vol%). Coupled with alkali-promoted Au/TS-1 catalysts, the system sustains > 90 % propylene oxide (PO) selectivity for 500 h, outperforming static mixers where activity halved within 100 h. This work pioneers a reactor-catalyst co-design strategy, decoupling safety constraints from reaction efficiency, and establishes a scalable platform for sustainable PO synthesis. Besides, the critical gaps in industrial-scale implementation of explosive gas-phase reactions is bridged.
{"title":"Micro-mixer combined with Au/TS-1 catalyst for improving the efficiency and safety of gas-phase propylene epoxidation","authors":"Yupeng Tian , Yujia Liu , Shoutao Ma , Wei Xu , Chenyang Zhao , Bing Sun","doi":"10.1016/j.cattod.2025.115661","DOIUrl":"10.1016/j.cattod.2025.115661","url":null,"abstract":"<div><div>This study introduces a heart-like micromixer reactor and Au/TS-1 catalyst to address the dual challenges of safety and efficiency in gas-phase propylene epoxidation using H<sub>2</sub> and O<sub>2</sub>. Conventional methods face inherent explosion risks and rapid catalyst deactivation due to sintering and coking. The microreactor architecture achieves over 99 % flame-quenching efficiency via sub-millisecond radical suppression and enhanced heat transfer, enabling safe operation with minimal inert gas dilution (N<sub>2</sub> < 70 vol%). Coupled with alkali-promoted Au/TS-1 catalysts, the system sustains > 90 % propylene oxide (PO) selectivity for 500 h, outperforming static mixers where activity halved within 100 h. This work pioneers a reactor-catalyst co-design strategy, decoupling safety constraints from reaction efficiency, and establishes a scalable platform for sustainable PO synthesis. Besides, the critical gaps in industrial-scale implementation of explosive gas-phase reactions is bridged.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115661"},"PeriodicalIF":5.3,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838677","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}
Electrocatalytic water splitting provides a promising approach to produce high-purity hydrogen. Nevertheless, the overall efficiency scalability of water electrolysis is severely constrained by the slow kinetics of the oxygen evolution process.Developing high-efficiency, durable and low-cost OER(oxygen evolution reaction) catalysts is therefore essential. Materials based on spinel Co3O4 have garnered a lot of interest as potential substitutes for rare Ir- and Ru-based oxides, owing to their tunable electronic structure, notable OER activity in acidic media, and the earth abundance of cobalt. This paper first reviews the research progress on Co₃O₄-based acidic OER electrocatalysts, three OER mechanisms have been summarized. It then highlights various modification strategies such as noble and non-noble metal doping, morphology control, reaction pathway regulation, heterostructure construction, and single-atom catalysis. Subsequently, the OER performance of Co₃O₄-based electrocatalysts was comparatively evaluated. Finally, current challenges and future research toward high-performance Co3O4-based acidic OER electrocatalysts are outlined.
{"title":"Recent progress of advanced Co3O4-based materials for electrocatalytic oxygen evolution reaction in acid","authors":"Zhe Wang, Yanwen Niu, Kaiyang Zhang, Rui Yao, Jinping Li, Guang Liu","doi":"10.1016/j.cattod.2025.115659","DOIUrl":"10.1016/j.cattod.2025.115659","url":null,"abstract":"<div><div>Electrocatalytic water splitting provides a promising approach to produce high-purity hydrogen. Nevertheless, the overall efficiency scalability of water electrolysis is severely constrained by the slow kinetics of the oxygen evolution process.Developing high-efficiency, durable and low-cost OER(oxygen evolution reaction) catalysts is therefore essential. Materials based on spinel Co<sub>3</sub>O<sub>4</sub> have garnered a lot of interest as potential substitutes for rare Ir- and Ru-based oxides, owing to their tunable electronic structure, notable OER activity in acidic media, and the earth abundance of cobalt. This paper first reviews the research progress on Co₃O₄-based acidic OER electrocatalysts, three OER mechanisms have been summarized. It then highlights various modification strategies such as noble and non-noble metal doping, morphology control, reaction pathway regulation, heterostructure construction, and single-atom catalysis. Subsequently, the OER performance of Co₃O₄-based electrocatalysts was comparatively evaluated. Finally, current challenges and future research toward high-performance Co<sub>3</sub>O<sub>4</sub>-based acidic OER electrocatalysts are outlined.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"466 ","pages":"Article 115659"},"PeriodicalIF":5.3,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799830","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}
The increasing presence of chemically stable and persistent dye rhodamine B in industrial wastewater poses significant environmental and health risk, necessitating its efficient and sustainable removal. Herein, carbon nano onions (CNOs) was synthesized utilizing used cooking oil (UCO) as a carbon source by the flame pyrolysis procedure. Cobalt (Co) and nitrogen (N) were incorporated in CNOs through a facile mechanochemical approach to obtain Co and N incorporated CNOs (Co-N/CNOs) catalysts. Various Co-N/CNOs catalysts were applied for the rhodamine B degradation in aqueous solution through advanced oxidation process (AOPs). The mechanochemical approach incorporating Co and N in CNOs yielded nanostructures with surface area 99 m2g−1. Structural analysis by XRD and XPS confirmed Co incorporation with multiple oxidation states (Co (0), Co (II), and Co (III)) in Co-N/CNOs. Raman analysis indicated Co doping introduced defects in adjacent carbon in CNOs, which served as active sites in activating H2O2 to •OH during the rhodamine B degradation reaction. The Co loading up to 11 wt% positively contributed to defects amount and hence, rhodamine B degradation efficiency. The catalyst 11Co-N/CNOs possessed highest amount of defect sites, leading to maximum rhodamine B degradation efficiency of 99.7 % under a low reaction time of 10 min and at 30 °C. The catalyst possessed promising stability up to use in four cycles at which, it could retain almost 90 % of the original activity. A kinetic analysis developed over the 11Co-N/CNOs catalyst suggested a pseudo-first-order reaction for the rhodamine B degradation process.
{"title":"Mechanochemical design of Co and N incorporated carbon nano onions for efficient rhodamine B degradation","authors":"Palak Jangir , Khush Vaishnav , Chakshu Chaplot , Gaurav Pandey , Kamlendra Awasthi , Ajay K. Dalai , Bikashbindu Das","doi":"10.1016/j.cattod.2025.115657","DOIUrl":"10.1016/j.cattod.2025.115657","url":null,"abstract":"<div><div>The increasing presence of chemically stable and persistent dye rhodamine B in industrial wastewater poses significant environmental and health risk, necessitating its efficient and sustainable removal. Herein, carbon nano onions (CNOs) was synthesized utilizing used cooking oil (UCO) as a carbon source by the flame pyrolysis procedure. Cobalt (Co) and nitrogen (N) were incorporated in CNOs through a facile mechanochemical approach to obtain Co and N incorporated CNOs (Co-N/CNOs) catalysts. Various Co-N/CNOs catalysts were applied for the rhodamine B degradation in aqueous solution through advanced oxidation process (AOPs). The mechanochemical approach incorporating Co and N in CNOs yielded nanostructures with surface area 99 m<sup>2</sup>g<sup>−1</sup>. Structural analysis by XRD and XPS confirmed Co incorporation with multiple oxidation states (Co (0), Co (II), and Co (III)) in Co-N/CNOs. Raman analysis indicated Co doping introduced defects in adjacent carbon in CNOs, which served as active sites in activating H<sub>2</sub>O<sub>2</sub> to •OH during the rhodamine B degradation reaction. The Co loading up to 11 wt% positively contributed to defects amount and hence, rhodamine B degradation efficiency. The catalyst 11Co-N/CNOs possessed highest amount of defect sites, leading to maximum rhodamine B degradation efficiency of 99.7 % under a low reaction time of 10 min and at 30 °C. The catalyst possessed promising stability up to use in four cycles at which, it could retain almost 90 % of the original activity. A kinetic analysis developed over the 11Co-N/CNOs catalyst suggested a pseudo-first-order reaction for the rhodamine B degradation process.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"465 ","pages":"Article 115657"},"PeriodicalIF":5.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787717","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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