Pub Date : 2025-03-01DOI: 10.1016/j.apcata.2025.120198
Junfang Ding , Changjin Xu , Hao Chai , Xinyi Yao , Yang Hao , Yingkang Yang , Xiaomin Sun , Guilan Fan , Shanghong Zeng
The surficial properties of heterogeneous catalysts are vital in determining their catalytic performance. Herein, we take K-CuOx/CeO2 as a typical composite to unveil the decisive role of surficial properties on the adsorption strengths of reactants, configurations of intermediates and desorption of products during CO preferential oxidation. Results show that adding K initially has minimal effect, but too much drastically reduces catalytic performance. Detailed analyses indicate adding K to CuOx/CeO2 catalyst increases the surficial basic sites, which not only inhibits O2 activation and CO2 desorption, but also reduces surface defects, Cu+ species and hydroxy species. Such a vast difference in adsorption behavior and surface species in turn lead to the transformation of intermediates from carboxylates to carbonates. DFT calculations further reveal that the barrier of rate-determining step for CuOx/CeO2 catalyst in carboxyl path is lower than that of K-CuOx/CeO2 in carbonate path, thus rendering a higher catalytic activity of CuOx/CeO2.
{"title":"Unveiling the decisive role of surficial properties on CuOx/CeO2 catalysts during CO preferential oxidation","authors":"Junfang Ding , Changjin Xu , Hao Chai , Xinyi Yao , Yang Hao , Yingkang Yang , Xiaomin Sun , Guilan Fan , Shanghong Zeng","doi":"10.1016/j.apcata.2025.120198","DOIUrl":"10.1016/j.apcata.2025.120198","url":null,"abstract":"<div><div>The surficial properties of heterogeneous catalysts are vital in determining their catalytic performance. Herein, we take K-CuO<sub><em>x</em></sub>/CeO<sub>2</sub> as a typical composite to unveil the decisive role of surficial properties on the adsorption strengths of reactants, configurations of intermediates and desorption of products during CO preferential oxidation. Results show that adding K initially has minimal effect, but too much drastically reduces catalytic performance. Detailed analyses indicate adding K to CuO<sub><em>x</em></sub>/CeO<sub>2</sub> catalyst increases the surficial basic sites, which not only inhibits O<sub>2</sub> activation and CO<sub>2</sub> desorption, but also reduces surface defects, Cu<sup>+</sup> species and hydroxy species. Such a vast difference in adsorption behavior and surface species in turn lead to the transformation of intermediates from carboxylates to carbonates. DFT calculations further reveal that the barrier of rate-determining step for CuO<sub><em>x</em></sub>/CeO<sub>2</sub> catalyst in carboxyl path is lower than that of K-CuO<sub><em>x</em></sub>/CeO<sub>2</sub> in carbonate path, thus rendering a higher catalytic activity of CuO<sub><em>x</em></sub>/CeO<sub>2</sub>.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120198"},"PeriodicalIF":4.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143528752","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}
Herein, a series of Sn-based catalysts supported on SBA-15 with temperature responsive ability to in situ construct acidic and basic sites are reported for efficient conversion of biomass-derived sugars into ethyl lactate (EL). Based on the investigation on the effects of the molar ratio of Cl/OH in Sn(OH)xCl2-x and the support types, it is found that Sn(OH)0.5Cl1.5@SBA-15 is an excellent catalyst in catalytic conversion of various sugars to EL, achieving a maximum EL yield of 68.1 % from sucrose. The in situ generated basic SnO sites play important roles in accelerating the retro-aldol condensation reaction, while the concomitantly released acidic sites (Sn2 +, SnCl+ and H+) could catalyze the reactions of hydrolysis, isomerization, intermolecular rearrangement and esterification to EL. Benefiting from the temperature responsive effect, not only can the reaction pathways be regulated toward high EL selectivity, but also the catalyst can be recycled easily. This research paves an avenue for exploring efficient catalysts for biomass valorization.
{"title":"Sn@SBA-15 with temperature responsive acid-base dual functional sites for catalyzing biomass-derived sugars to ethyl lactate","authors":"Yifan Liu, Jiangang Wang, Yuhan Liu, Yuan Zhang, Hongzi Tan, Hongyou Cui","doi":"10.1016/j.apcata.2025.120187","DOIUrl":"10.1016/j.apcata.2025.120187","url":null,"abstract":"<div><div>Herein, a series of Sn-based catalysts supported on SBA-15 with temperature responsive ability to in situ construct acidic and basic sites are reported for efficient conversion of biomass-derived sugars into ethyl lactate (EL). Based on the investigation on the effects of the molar ratio of Cl/OH in Sn(OH)<sub><em>x</em></sub>Cl<sub><em>2-x</em></sub> and the support types, it is found that Sn(OH)<sub>0.5</sub>Cl<sub>1.5</sub>@SBA-15 is an excellent catalyst in catalytic conversion of various sugars to EL, achieving a maximum EL yield of 68.1 % from sucrose. The in situ generated basic SnO sites play important roles in accelerating the retro-aldol condensation reaction, while the concomitantly released acidic sites (Sn<sup>2 +</sup>, SnCl<sup>+</sup> and H<sup>+</sup>) could catalyze the reactions of hydrolysis, isomerization, intermolecular rearrangement and esterification to EL. Benefiting from the temperature responsive effect, not only can the reaction pathways be regulated toward high EL selectivity, but also the catalyst can be recycled easily. This research paves an avenue for exploring efficient catalysts for biomass valorization.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120187"},"PeriodicalIF":4.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143528753","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 : 2025-02-25DOI: 10.1016/j.apcata.2025.120188
Bei Jiang , Ling Zhang , Wenjing Wang , Xin Qin , Shenyan Xu , Chunyu Che , Chuanqi Zhang , Wenzhong Wang
Continuous flow reactors have seldom been employed in investigations concerning 5-hydroxymethylfurfural (HMF) oxidation reactions. The root cause lies in the fact that, at atmospheric pressure, the solution exhibits a rather low oxygen content. In this research, we present a Ru-loaded manganese oxide octahedral molecular sieve (OMS-2) catalyst. Remarkably, this catalyst has exhibited the ability to achieve a 100 % conversion rate of HMF and attain a 94.5 % yield of FDCA under ambient air conditions within a continuous flow reactor. This can be mainly attributed to the superior oxygen adsorption and activation capacity of 0.05Ru-OMS-2. Thanks to this, it exhibits good performance even under hypoxic conditions. The combined results of EPR and XPS clearly showed that the Ru in the catalyst not only boosts the adsorption and transformation of O₂ but also weakens the Mn-O bond in the carrier, thus enhancing the activity of lattice oxygen.
{"title":"Preparation of 2,5-furandicarboxylic acid through continuous flow oxidation of 5-hydroxymethylfurfural under hypoxic condition","authors":"Bei Jiang , Ling Zhang , Wenjing Wang , Xin Qin , Shenyan Xu , Chunyu Che , Chuanqi Zhang , Wenzhong Wang","doi":"10.1016/j.apcata.2025.120188","DOIUrl":"10.1016/j.apcata.2025.120188","url":null,"abstract":"<div><div>Continuous flow reactors have seldom been employed in investigations concerning 5-hydroxymethylfurfural (HMF) oxidation reactions. The root cause lies in the fact that, at atmospheric pressure, the solution exhibits a rather low oxygen content. In this research, we present a Ru-loaded manganese oxide octahedral molecular sieve (OMS-2) catalyst. Remarkably, this catalyst has exhibited the ability to achieve a 100 % conversion rate of HMF and attain a 94.5 % yield of FDCA under ambient air conditions within a continuous flow reactor. This can be mainly attributed to the superior oxygen adsorption and activation capacity of 0.05Ru-OMS-2. Thanks to this, it exhibits good performance even under hypoxic conditions. The combined results of EPR and XPS clearly showed that the Ru in the catalyst not only boosts the adsorption and transformation of O₂ but also weakens the Mn-O bond in the carrier, thus enhancing the activity of lattice oxygen.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120188"},"PeriodicalIF":4.7,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509501","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 : 2025-02-24DOI: 10.1016/j.apcata.2025.120185
Mengyao Luo , Longli Bo , Sining Huang , Haiguang Wang , Zhiyun Yang , Danjun Wang , Ying Yang , Zhe Li , Lu Wang
Adding polyethylene glycol (PEG) can lessen the shedding of coating and improve the dispersion of active particles for monolithic catalysts. In this study, a series of Cu-Mn-Ce-Ox(Px)/TiO2(Px)/CH catalysts were prepared with different PEG molecular weights (Px, x = 200, 1000, and 2000) to explore the effect of Px addition on the structure and activity of the catalysts in microwave catalytic combustion of toluene. The research showed that Px addition (1 wt% dosage to titanium sol) to coating reduced the particle size of titanium sol and decreased the shedding rate of TiO2 coating 0.9–0.93 %, and Px addition (3 wt% dosage to CH's water absorption) to active components further lessened the shedding rate of the catalysts 1.93–2.04 %. Under an initial toluene concentration of 1500 mg/m3 and a gas hourly space velocity of 2260 h−1, Cu-Mn-Ce-Ox(P1000)/TiO2(P1000)/CH owned the highest catalytic activity and its complete removal temperature (TR100) and mineralization temperature (TM100) to toluene were 180℃ and 218℃, respectively, which were lower 33℃ and 16℃, 56℃ and 58℃ than Cu-Mn-Ce-Ox/TiO2(P1000)/CH and Cu-Mn-Ce-Ox/TiO2/CH catalysts separately, and its activity maintained steadily with toluene removal efficiencies of 99–91 % over 12 h. The improved activity is attributed to the uniform dispersion of active particles, larger specific surface area, and increased adsorbed oxygen, facilitated by pore-forming and steric-hindrance effects of Px. Electron transfer among Mn4+/Mn3+/Mn2+, Cu2+/Cu+, and Ce4+/Ce3+ promoted the oxidation of toluene under microwave irradiation. Therefore, the research provides technological support for developing transition metals-based catalysts for industrial VOC waste gas treatment.
{"title":"Effect of polyethylene glycol addition on Cu-Mn-Ce-Ox/TiO2/CH catalyst in microwave catalytic combustion of toluene","authors":"Mengyao Luo , Longli Bo , Sining Huang , Haiguang Wang , Zhiyun Yang , Danjun Wang , Ying Yang , Zhe Li , Lu Wang","doi":"10.1016/j.apcata.2025.120185","DOIUrl":"10.1016/j.apcata.2025.120185","url":null,"abstract":"<div><div>Adding polyethylene glycol (PEG) can lessen the shedding of coating and improve the dispersion of active particles for monolithic catalysts. In this study, a series of Cu-Mn-Ce-O<sub><em>x</em></sub>(P<sub><em>x</em></sub>)/TiO<sub>2</sub>(P<sub><em>x</em></sub>)/CH catalysts were prepared with different PEG molecular weights (P<sub><em>x</em></sub>, x = 200, 1000, and 2000) to explore the effect of P<sub><em>x</em></sub> addition on the structure and activity of the catalysts in microwave catalytic combustion of toluene. The research showed that P<sub><em>x</em></sub> addition (1 wt% dosage to titanium sol) to coating reduced the particle size of titanium sol and decreased the shedding rate of TiO<sub>2</sub> coating 0.9–0.93 %, and P<sub><em>x</em></sub> addition (3 wt% dosage to CH's water absorption) to active components further lessened the shedding rate of the catalysts 1.93–2.04 %. Under an initial toluene concentration of 1500 mg/m<sup>3</sup> and a gas hourly space velocity of 2260 h<sup>−1</sup>, Cu-Mn-Ce-O<sub><em>x</em></sub>(P<sub>1000</sub>)/TiO<sub>2</sub>(P<sub>1000</sub>)/CH owned the highest catalytic activity and its complete removal temperature (T<sub>R100</sub>) and mineralization temperature (T<sub>M100</sub>) to toluene were 180℃ and 218℃, respectively, which were lower 33℃ and 16℃, 56℃ and 58℃ than Cu-Mn-Ce-O<sub><em>x</em></sub>/TiO<sub>2</sub>(P<sub>1000</sub>)/CH and Cu-Mn-Ce-O<sub><em>x</em></sub>/TiO<sub>2</sub>/CH catalysts separately, and its activity maintained steadily with toluene removal efficiencies of 99–91 % over 12 h. The improved activity is attributed to the uniform dispersion of active particles, larger specific surface area, and increased adsorbed oxygen, facilitated by pore-forming and steric-hindrance effects of P<sub><em>x</em></sub>. Electron transfer among Mn<sup>4+</sup>/Mn<sup>3+</sup>/Mn<sup>2+</sup>, Cu<sup>2+</sup>/Cu<sup>+</sup>, and Ce<sup>4+</sup>/Ce<sup>3+</sup> promoted the oxidation of toluene under microwave irradiation. Therefore, the research provides technological support for developing transition metals-based catalysts for industrial VOC waste gas treatment.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120185"},"PeriodicalIF":4.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509500","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 : 2025-02-24DOI: 10.1016/j.apcata.2025.120184
Zhe Tang , Jilei Liang , Jianhui Su
A easy-to-handle and bi-functional solid water-tolerant catalyst with the balance of Brønsted acid site ( BAS) and Lewis acid site (LAS) is crucial for the efficient conversion of glucose into 5-hydroxymethylfurfural (HMF). In the work, the AACH@γ-AlOOH (designated as Ny@γ-AlOOH) catalysts were synthesized through the in-situ AACH substitution of γ-AlOOH, where the AlO6 octahedral units served as the wate - tolerant LAS with mild acid strength, while the unsaturated AlO5 pentahedral units acted as the weak BAS, together forming Lewis - Brønsted acid pairs at molecular- level proximity. Glucose turnover and HMF selectivity were enhanced due to the rapid fructose transfer from LAS to the adjacent BAS for its dehydration to HMF, facilitating LAS liberation for another glucose turnover. Under an optimized catalyst N4/11@γ-AlOOH, a high HMF yield of 73.8 % was obtained in biphasic system of 1-butanol / H2O - NaCl (20 wt%) at 140 °C for 3 h.
{"title":"High efficient production of 5-hydroxymethyl-furfural from glucose over AACH @ γ-AlOOH catalyst: Insights into structure, acidic properties and performance","authors":"Zhe Tang , Jilei Liang , Jianhui Su","doi":"10.1016/j.apcata.2025.120184","DOIUrl":"10.1016/j.apcata.2025.120184","url":null,"abstract":"<div><div>A easy-to-handle and bi-functional solid water-tolerant catalyst with the balance of Brønsted acid site ( BAS) and Lewis acid site (LAS) is crucial for the efficient conversion of glucose into 5-hydroxymethylfurfural (HMF). In the work, the AACH@γ-AlOOH (designated as N<sub>y</sub>@γ-AlOOH) catalysts were synthesized through the in-situ AACH substitution of γ-AlOOH, where the AlO<sub>6</sub> octahedral units served as the wate - tolerant LAS with mild acid strength, while the unsaturated AlO<sub>5</sub> pentahedral units acted as the weak BAS, together forming Lewis - Brønsted acid pairs at molecular- level proximity. Glucose turnover and HMF selectivity were enhanced due to the rapid fructose transfer from LAS to the adjacent BAS for its dehydration to HMF, facilitating LAS liberation for another glucose turnover. Under an optimized catalyst N<sub>4/11</sub>@γ-AlOOH, a high HMF yield of 73.8 % was obtained in biphasic system of 1-butanol / H<sub>2</sub>O - NaCl (20 wt%) at 140 °C for 3 h.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120184"},"PeriodicalIF":4.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509354","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 : 2025-02-20DOI: 10.1016/j.apcata.2025.120181
Sara Sumbal, Justyna Łuczak, Afaq Hassan, Marek Lieder
Single metal layered α-Ni(OH)2, β-Ni(OH)2 or dual metal layered NiCu hydroxides were hydrothermally deposited on nickel foam (NF) and investigated for electrochemical oxidation of ammonia. Copper induced conversion of hydrotalcite (α-Ni(OH)2) phase into the mixed hydrotalcite/brucite (α/β-NiCu) structure, which is distinguished by smaller stacks and larger interplanar distances, demonstrated the highest catalytic performance. Copper inclusion resulted in two-fold increase in the current density (to 55.2 mA/cm2 at 1.55 V vs RHE for α/β-NiCu(1/1)) as well as significant increase in the electrochemical active surface area (387.5 cm2) and turnover frequency (0.56 1/cm2). The presence of Cu does not affect the onset potential of the reaction but elevated the overpotential of water oxidation, thereby increasing N2 selectivity. We proposed formation of temporary vacancies on the copper sites during AOR, which allowed the adsorption of OH followed by their coupling with hydrogen atoms derived from NHx molecules bound to nickel sites (dual-sites mechanism).
{"title":"Role of Cu and Ni in dual sites layered electrocatalysts for ammonia electrooxidation","authors":"Sara Sumbal, Justyna Łuczak, Afaq Hassan, Marek Lieder","doi":"10.1016/j.apcata.2025.120181","DOIUrl":"10.1016/j.apcata.2025.120181","url":null,"abstract":"<div><div>Single metal layered α-Ni(OH)<sub>2</sub>, β-Ni(OH)<sub>2</sub> or dual metal layered NiCu hydroxides were hydrothermally deposited on nickel foam (NF) and investigated for electrochemical oxidation of ammonia. Copper induced conversion of hydrotalcite (α-Ni(OH)<sub>2</sub>) phase into the mixed hydrotalcite/brucite (α/β-NiCu) structure, which is distinguished by smaller stacks and larger interplanar distances, demonstrated the highest catalytic performance. Copper inclusion resulted in two-fold increase in the current density (to 55.2 mA/cm<sup>2</sup> at 1.55 V <em>vs</em> RHE for α/β-NiCu<sub>(1/1)</sub>) as well as significant increase in the electrochemical active surface area (387.5 cm<sup>2</sup>) and turnover frequency (0.56 1/cm<sup>2</sup>). The presence of Cu does not affect the onset potential of the reaction but elevated the overpotential of water oxidation, thereby increasing N<sub>2</sub> selectivity. We proposed formation of temporary vacancies on the copper sites during AOR, which allowed the adsorption of OH followed by their coupling with hydrogen atoms derived from NH<sub>x</sub> molecules bound to nickel sites (dual-sites mechanism).</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120181"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511662","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}
To enhance the skeletal isomerization activity of the catalyst and increase the yield of branch chain unsaturated fatty acids (BUFAs) from oleic acid, a series of silica-coated ZSM-22 with different silica content were developed by crystal overgrowth. The patterns of XRD exposed that zeolitic framework structures of ZSM-22 were kept after silica coating. 2,6-lutidine adsorption FT-IR spectroscopy revealed that the acid sites on the external surface of silica-coated ZSM-22 samples were partially covered by silica layers. Regarding the influence of silica coating amount, 20Si·HZ-22(60) with 20 % silica content had a high BUFAs yield of above 80 % and more efficiently inhibited the formation of dimer acids compared to parent ZSM-22(60) without silica coating. Additionally, the suppression of dimer acid formation makes the catalyst less prone to deactivation.
{"title":"Skeletal isomerization of oleic acid on silica-coated ZSM-22","authors":"Xinyu Wei, Mingming Peng, Toshiya Tsunakawa, Yuyang Jia, Kenji Kamiya, Eika W. Qian","doi":"10.1016/j.apcata.2025.120182","DOIUrl":"10.1016/j.apcata.2025.120182","url":null,"abstract":"<div><div>To enhance the skeletal isomerization activity of the catalyst and increase the yield of branch chain unsaturated fatty acids (BUFAs) from oleic acid, a series of silica-coated ZSM-22 with different silica content were developed by crystal overgrowth. The patterns of XRD exposed that zeolitic framework structures of ZSM-22 were kept after silica coating. 2,6-lutidine adsorption FT-IR spectroscopy revealed that the acid sites on the external surface of silica-coated ZSM-22 samples were partially covered by silica layers. Regarding the influence of silica coating amount, 20Si·HZ-22(60) with 20 % silica content had a high BUFAs yield of above 80 % and more efficiently inhibited the formation of dimer acids compared to parent ZSM-22(60) without silica coating. Additionally, the suppression of dimer acid formation makes the catalyst less prone to deactivation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"696 ","pages":"Article 120182"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519958","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 : 2025-02-20DOI: 10.1016/j.apcata.2025.120180
Yucheng Liu , Xinzhi Zang , Songjian Zhao , Zixuan Wang , Wenqiang Wang , Jingxin Xu , Sheng Wang , Zhaolian Ye
Dielectric barrier discharge (DBD) plasma catalytic technology is considered as one of the most effective methods for elimination of diluted volatile organic compounds (VOCs) due to its advantages of high efficiency, low cost, and wide applicability. The design of highly efficient catalytic materials is a notable challenge for this technology. In this study, Ti3C2Tx, GO, and NiMn2O4, which possess a large specific surface area and high electron transport properties, were introduced as catalyst supports. These materials were combined with CoMn-BTC to synthesize three types of supported composite catalysts, which were used for the DBD-assisted VOCs degradation. Characterization analyses, including XRD, FTIR and SEM, indicated that CoMn-BTC was successfully integrated with the three supports. The large specific surface area and more oxygen vacancy for CoMn-BTC/Ti3C2Tx than bulk CoMn-BTC explained the enhanced toluene removal efficiency and mineralization, CO2 selectivity, along with suppression of undesirable O3 and NOx. Characterization of CoMn-BTC/Ti3C2Tx catalysts before and after the plasma catalytic process indicated that high adsorbed oxygen species and the redox cycles between Co3 +/Co2+ and Mn2+/(Mn4+, Mn3+) species can effectively promote toluene and intermediates oxidation. Furthermore, GC-MS analysis of the organic by-products in the effluent gas revealed that the amounts of intermediates such as nitrophenol reduced in the CoMn-BTC/Ti3C2Tx compared with CoMn-BTC, further demonstrating that CoMn-BTC/Ti3C2Tx had excellent catalytic activity. At last, the possible reaction pathways of toluene degradation in plasma-catalytic system was proposed in combination with analysis results of GC-MS, optical emission spectroscopy and properties of the catalyst before and after discharge reaction.
{"title":"Degradation of toluene by DBD plasma catalytic technology with CoMn-BTC/ Ti3C2Tx composites","authors":"Yucheng Liu , Xinzhi Zang , Songjian Zhao , Zixuan Wang , Wenqiang Wang , Jingxin Xu , Sheng Wang , Zhaolian Ye","doi":"10.1016/j.apcata.2025.120180","DOIUrl":"10.1016/j.apcata.2025.120180","url":null,"abstract":"<div><div>Dielectric barrier discharge (DBD) plasma catalytic technology is considered as one of the most effective methods for elimination of diluted volatile organic compounds (VOCs) due to its advantages of high efficiency, low cost, and wide applicability. The design of highly efficient catalytic materials is a notable challenge for this technology. In this study, Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>, GO, and NiMn<sub>2</sub>O<sub>4</sub>, which possess a large specific surface area and high electron transport properties, were introduced as catalyst supports. These materials were combined with CoMn-BTC to synthesize three types of supported composite catalysts, which were used for the DBD-assisted VOCs degradation. Characterization analyses, including XRD, FTIR and SEM, indicated that CoMn-BTC was successfully integrated with the three supports. The large specific surface area and more oxygen vacancy for CoMn-BTC/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> than bulk CoMn-BTC explained the enhanced toluene removal efficiency and mineralization, CO<sub>2</sub> selectivity, along with suppression of undesirable O<sub>3</sub> and NO<sub>x</sub>. Characterization of CoMn-BTC/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> catalysts before and after the plasma catalytic process indicated that high adsorbed oxygen species and the redox cycles between Co<sup>3 +</sup>/Co<sup>2+</sup> and Mn<sup>2+</sup>/(Mn<sup>4+</sup>, Mn<sup>3+</sup>) species can effectively promote toluene and intermediates oxidation. Furthermore, GC-MS analysis of the organic by-products in the effluent gas revealed that the amounts of intermediates such as nitrophenol reduced in the CoMn-BTC/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> compared with CoMn-BTC, further demonstrating that CoMn-BTC/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> had excellent catalytic activity. At last, the possible reaction pathways of toluene degradation in plasma-catalytic system was proposed in combination with analysis results of GC-MS, optical emission spectroscopy and properties of the catalyst before and after discharge reaction.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120180"},"PeriodicalIF":4.7,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480443","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 : 2025-02-18DOI: 10.1016/j.apcata.2025.120170
Xiaolin Jiang , Liguang Zhang , Shenglong Jiang , Liwei Sun , Yaru Zou , Yuehui Li
Utilizing CO2 as an abundant and low-cost C1 resource for the production of value-added chemicals is of significant industrial interest. This work introduces a metal-free cyclization of CO2 and epoxides into cyclic carbonates, catalyzed by electron-deficient, fluorine-substituted boronic acids under mild conditions. The catalysts demonstrate high activity and selectivity under mild condtions in non-polar solvents, with excellent compatibility with various functional groups such as heterocycle, alkene, phthalimide and chloride (13 examples, 53–95 % yields). The electron deficiency by F-substitution and the use of non-polar solvents enhance B-O interactions, allowing excellent catalytic performance and 6 times of catalyst recycling. This work highlights an effective strategy for CO2 utilization, advancing recyclable boronic acid catalysts in green chemistry.
{"title":"Electron-deficient boronic acid catalyzed cyclization of CO2 and epoxides","authors":"Xiaolin Jiang , Liguang Zhang , Shenglong Jiang , Liwei Sun , Yaru Zou , Yuehui Li","doi":"10.1016/j.apcata.2025.120170","DOIUrl":"10.1016/j.apcata.2025.120170","url":null,"abstract":"<div><div>Utilizing CO<sub>2</sub> as an abundant and low-cost C1 resource for the production of value-added chemicals is of significant industrial interest. This work introduces a metal-free cyclization of CO<sub>2</sub> and epoxides into cyclic carbonates, catalyzed by electron-deficient, fluorine-substituted boronic acids under mild conditions. The catalysts demonstrate high activity and selectivity under mild condtions in non-polar solvents, with excellent compatibility with various functional groups such as heterocycle, alkene, phthalimide and chloride (13 examples, 53–95 % yields). The electron deficiency by F-substitution and the use of non-polar solvents enhance B-O interactions, allowing excellent catalytic performance and 6 times of catalyst recycling. This work highlights an effective strategy for CO<sub>2</sub> utilization, advancing recyclable boronic acid catalysts in green chemistry.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120170"},"PeriodicalIF":4.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463713","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 : 2025-02-18DOI: 10.1016/j.apcata.2025.120171
Ning Li , Jingbo Li , Jianqiao Zhao , Huili Liu , Jiayun Tang , Ruizhi Chu , Xianliang Meng , Weisong Li , Xiao Li
This paper prepared two different occurrence state of cobalt-modified SAPO-34 by impregnation and in situ synthesis, investigating effects on methanol-to-olefin reaction performance. The results showed that the Co modification improved the pore structure, increased the weak acid concentration, and extended the catalytic lifetime of SAPO-34. Among them, the framework-substituted Co-based zeolite has higher olefin selectivity and longer life than SAPO-34 with metal Co on the surface. Besides, the key coke precursors like methyl-substituted benzenes were preferentially deposited in micropores and strong acid sites, and significantly promote the generation of condensed ring aromatic hydrocarbons. While the relatively large mesopore volume and slightly lower strong acid concentration of the framework-substituted Co-based zeolite can synergize reduce the formation rate of coke and inhibit the formation of polycyclic aromatic hydrocarbons, thus improving SAPO-34's anti-coking performance. This revelation sparked a novel concept aimed at enhancing the anti-coking capabilities of metal-based zeolites.
{"title":"Effect of Co occurrence state on catalytic and coke resistance performance of SAPO-34 in MTO reaction","authors":"Ning Li , Jingbo Li , Jianqiao Zhao , Huili Liu , Jiayun Tang , Ruizhi Chu , Xianliang Meng , Weisong Li , Xiao Li","doi":"10.1016/j.apcata.2025.120171","DOIUrl":"10.1016/j.apcata.2025.120171","url":null,"abstract":"<div><div>This paper prepared two different occurrence state of cobalt-modified SAPO-34 by impregnation and in situ synthesis, investigating effects on methanol-to-olefin reaction performance. The results showed that the Co modification improved the pore structure, increased the weak acid concentration, and extended the catalytic lifetime of SAPO-34. Among them, the framework-substituted Co-based zeolite has higher olefin selectivity and longer life than SAPO-34 with metal Co on the surface. Besides, the key coke precursors like methyl-substituted benzenes were preferentially deposited in micropores and strong acid sites, and significantly promote the generation of condensed ring aromatic hydrocarbons. While the relatively large mesopore volume and slightly lower strong acid concentration of the framework-substituted Co-based zeolite can synergize reduce the formation rate of coke and inhibit the formation of polycyclic aromatic hydrocarbons, thus improving SAPO-34's anti-coking performance. This revelation sparked a novel concept aimed at enhancing the anti-coking capabilities of metal-based zeolites.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"695 ","pages":"Article 120171"},"PeriodicalIF":4.7,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463712","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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