Pub Date : 2024-07-13DOI: 10.1007/s10562-024-04756-1
Allam Djaouida, Hocine Smain, Thomas Sébastien, Parkhomenko Ksenia, Roger Anne-Cécile, Kaci Samira
Ternary Cu/ZnO/Al2O3 and Cu/ZnO/CeO2 catalysts were prepared by polyol method and tested for gas-phase low-temperature methanol synthesis from hydrogenation of CO2. The catalysts were characterized by N2 physisorption, SEM–EDX, XRD, H2-TPR and XPS. The activity of the catalysts was evaluated in a fixed-bed micro-reactor at atmospheric pressure and 40 bar at different reaction temperatures, and H2/CO2 ratio of 3:1. The results showed that the nature of the promoter influenced the physicochemical properties of the catalysts as well as the catalytic activity and product selectivity. Compared with ternary Cu/ZnO/Al2O3 catalyst, Cu/ZnO/CeO2 catalyst indicated that modifcation of CuO/ZnO catalyst with CeO2 promoted the CuO dispersion, reduced the CuO crystallite size, decreased the reduction temperature of highly dispersed CuO, decreased the activation energy and improved the catalytic activity of the Cu/ZnO/CeO2 catalyst.
{"title":"Comparative Study on the Effect of Cerina and Alumina on the Catalytic Activity of CuO-ZnO Based Catalyst in CO2 Hydrogenation to Methanol","authors":"Allam Djaouida, Hocine Smain, Thomas Sébastien, Parkhomenko Ksenia, Roger Anne-Cécile, Kaci Samira","doi":"10.1007/s10562-024-04756-1","DOIUrl":"10.1007/s10562-024-04756-1","url":null,"abstract":"<div><p>Ternary Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> and Cu/ZnO/CeO<sub>2</sub> catalysts were prepared by polyol method and tested for gas-phase low-temperature methanol synthesis from hydrogenation of CO<sub>2</sub>. The catalysts were characterized by N<sub>2</sub> physisorption, SEM–EDX, XRD, H<sub>2</sub>-TPR and XPS. The activity of the catalysts was evaluated in a fixed-bed micro-reactor at atmospheric pressure and 40 bar at different reaction temperatures, and H<sub>2</sub>/CO<sub>2</sub> ratio of 3:1. The results showed that the nature of the promoter influenced the physicochemical properties of the catalysts as well as the catalytic activity and product selectivity. Compared with ternary Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> catalyst, Cu/ZnO/CeO<sub>2</sub> catalyst indicated that modifcation of CuO/ZnO catalyst with CeO<sub>2</sub> promoted the CuO dispersion, reduced the CuO crystallite size, decreased the reduction temperature of highly dispersed CuO, decreased the activation energy and improved the catalytic activity of the Cu/ZnO/CeO<sub>2</sub> catalyst.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5849 - 5864"},"PeriodicalIF":2.3,"publicationDate":"2024-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-09DOI: 10.1007/s10562-024-04733-8
Long Ding, Hexi Zhao, Lei Ni, Zhongbin Wang, Lixin Qian, Hongming Long
The emission of CO in sintering flue gas contributes to environmental pollution and energy wastage. Achieving full oxidation of CO presents a viable strategy for elevating the sintering flue gas temperature by over 50°C, thereby significantly reducing energy consumption during the heating of flue gas in NH3-SCR denitrification systems. In this work, MnCeOx catalysts were synthesized under various conditions, including different calcination temperatures, durations, and molar ratios. Their catalytic activity and resistance to H2O were evaluated under simulated sintering flue gas conditions at different temperatures. Our findings indicated that the M8C1 catalyst exhibited exceptional activity, achieving CO conversion rates exceeding 95% within 125–250°C. However, the catalytic activity experienced a notable decline during the H2O resistance test at 150°C, while remaining unaffected at 250°C. Investigating the inhibition mechanism of H2O on CO oxidation at varying temperatures through H2-TPR, O2-TPD, and in situ DRIFTS. At lower temperatures (150°C), CO and O2 adsorption on the catalyst surface led to the formation of CO2, with O2 adsorption exerting a more significant influence on activity, consistent with the Langmuir–Hinshelwood mechanism. Introduction of H2O into the flue gas resulted in the formation of OH−, which competed with CO and O2 for adsorption on the catalyst surface, thereby diminishing catalyst oxidation activity due to competitive adsorption hindering CO and O2 adsorption. Conversely, at higher temperatures (250°C), the reaction process between CO and lattice oxygen to produce CO2 followed the Mars-van Krevelen mechanism. Notably, at these temperatures, no adsorbed OH− were detected on the catalyst surface, leaving the activity unaffected. Based on our research, employing the MnCeOx catalyst during the high-temperature stage in conjunction with the NH3-SCR catalyst is recommended for enhanced CO oxidation efficiency in sintering flue gas treatment processes.
Graphical Abstract
烧结烟气中 CO 的排放会造成环境污染和能源浪费。实现 CO 的完全氧化是将烧结烟气温度提高 50°C 以上的可行策略，从而显著降低 NH3-SCR 脱硝系统烟气加热过程中的能耗。在这项工作中，MnCeOx 催化剂是在不同条件下合成的，包括不同的煅烧温度、煅烧时间和摩尔比。在不同温度下的模拟烧结烟气条件下，对催化剂的催化活性和抗 H2O 能力进行了评估。研究结果表明，M8C1 催化剂具有优异的活性，在 125-250°C 的温度范围内，CO 转化率超过 95%。然而，在 150°C 的耐 H2O 试验中，催化活性明显下降，而在 250°C 时则不受影响。通过 H2-TPR、O2-TPD 和原位 DRIFTS，研究不同温度下 H2O 对 CO 氧化的抑制机制。在较低温度（150°C）下，CO 和 O2 在催化剂表面的吸附导致 CO2 的形成，其中 O2 的吸附对活性的影响更为显著，这与 Langmuir-Hinshelwood 机制一致。在烟气中引入 H2O 会形成 OH-，与 CO 和 O2 竞争吸附在催化剂表面，由于竞争吸附阻碍了 CO 和 O2 的吸附，从而降低了催化剂的氧化活性。相反，在较高温度（250°C）下，CO 和晶格氧生成 CO2 的反应过程遵循 Mars-van Krevelen 机理。值得注意的是，在这些温度下，催化剂表面未检测到吸附的 OH-，活性未受影响。根据我们的研究，建议在高温阶段将 MnCeOx 催化剂与 NH3-SCR 催化剂结合使用，以提高烧结烟气处理工艺中的 CO 氧化效率。 图文摘要
{"title":"Inhibition Mechanism of H2O on CO Oxidation Over CeMnOx Catalyst in Iron Ore Sintering Flue Gas","authors":"Long Ding, Hexi Zhao, Lei Ni, Zhongbin Wang, Lixin Qian, Hongming Long","doi":"10.1007/s10562-024-04733-8","DOIUrl":"10.1007/s10562-024-04733-8","url":null,"abstract":"<div><p>The emission of CO in sintering flue gas contributes to environmental pollution and energy wastage. Achieving full oxidation of CO presents a viable strategy for elevating the sintering flue gas temperature by over 50°C, thereby significantly reducing energy consumption during the heating of flue gas in NH<sub>3</sub>-SCR denitrification systems. In this work, MnCeOx catalysts were synthesized under various conditions, including different calcination temperatures, durations, and molar ratios. Their catalytic activity and resistance to H<sub>2</sub>O were evaluated under simulated sintering flue gas conditions at different temperatures. Our findings indicated that the M<sub>8</sub>C<sub>1</sub> catalyst exhibited exceptional activity, achieving CO conversion rates exceeding 95% within 125–250°C. However, the catalytic activity experienced a notable decline during the H<sub>2</sub>O resistance test at 150°C, while remaining unaffected at 250°C. Investigating the inhibition mechanism of H<sub>2</sub>O on CO oxidation at varying temperatures through H<sub>2</sub>-TPR, O<sub>2</sub>-TPD, and in situ DRIFTS. At lower temperatures (150°C), CO and O<sub>2</sub> adsorption on the catalyst surface led to the formation of CO<sub>2</sub>, with O<sub>2</sub> adsorption exerting a more significant influence on activity, consistent with the Langmuir–Hinshelwood mechanism. Introduction of H<sub>2</sub>O into the flue gas resulted in the formation of OH<sup>−</sup>, which competed with CO and O<sub>2</sub> for adsorption on the catalyst surface, thereby diminishing catalyst oxidation activity due to competitive adsorption hindering CO and O<sub>2</sub> adsorption. Conversely, at higher temperatures (250°C), the reaction process between CO and lattice oxygen to produce CO<sub>2</sub> followed the Mars-van Krevelen mechanism. Notably, at these temperatures, no adsorbed OH<sup>−</sup> were detected on the catalyst surface, leaving the activity unaffected. Based on our research, employing the MnCeOx catalyst during the high-temperature stage in conjunction with the NH<sub>3</sub>-SCR catalyst is recommended for enhanced CO oxidation efficiency in sintering flue gas treatment processes.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5838 - 5848"},"PeriodicalIF":2.3,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-08DOI: 10.1007/s10562-024-04765-0
Simanye Sam, Babatope O. Ojo, Soraya P. Malinga, Nonhlangabezo Mabuba
Organic compounds of various classes have been identified as major pollutants commonly detected in several environmental freshwaters. As a potential solution, electrospun mat-like nanofibers comprising polyvinylidene fluoride (PVDF) nanofibers and kaolin clay composite were synthesized for the degradation of methylene blue dye in wastewater using piezocatalytic technique. The kaolin/PVDF composites were characterized with SEM, XRD, FTIR, Chronoamperometry and electrochemical impedance spectroscopy. The poling of the piezoelectric charges of the electrospun mat-like nanofibers, enhanced by the presence of the crystalline nature of the kaolin clay occasioned the generation of reactive species upon exposure to ultrasonic vibration. Moreover, ultrasound waves in the system prevented passivation of the mat’s active surface during piezocatalysis through continuous cleaning action. A degradation efficiency of 100% was obtained from the degradation of methylene blue dye using the synthesized kaolin/PVDF composites during piezocatalysis. This result positions the nanofiber as an effective catalyst in wastewater treatment applications.
{"title":"A Piezoelectric Electrospun Nanofiber mat (Kaolin/PVDF) for the Degradation of Methylene Blue in Water","authors":"Simanye Sam, Babatope O. Ojo, Soraya P. Malinga, Nonhlangabezo Mabuba","doi":"10.1007/s10562-024-04765-0","DOIUrl":"10.1007/s10562-024-04765-0","url":null,"abstract":"<div><p>Organic compounds of various classes have been identified as major pollutants commonly detected in several environmental freshwaters. As a potential solution, electrospun mat-like nanofibers comprising polyvinylidene fluoride (PVDF) nanofibers and kaolin clay composite were synthesized for the degradation of methylene blue dye in wastewater using piezocatalytic technique. The kaolin/PVDF composites were characterized with SEM, XRD, FTIR, Chronoamperometry and electrochemical impedance spectroscopy. The poling of the piezoelectric charges of the electrospun mat-like nanofibers, enhanced by the presence of the crystalline nature of the kaolin clay occasioned the generation of reactive species upon exposure to ultrasonic vibration. Moreover, ultrasound waves in the system prevented passivation of the mat’s active surface during piezocatalysis through continuous cleaning action. A degradation efficiency of 100% was obtained from the degradation of methylene blue dye using the synthesized kaolin/PVDF composites during piezocatalysis. This result positions the nanofiber as an effective catalyst in wastewater treatment applications.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5817 - 5829"},"PeriodicalIF":2.3,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10562-024-04765-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ammonia (NH3) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C3N4 (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH3 yield rate: 15.2 μg h−1 mgcat−1, Faradaic efficiency: 7.1%) at -0.4 V (vs. RHE) than others. It is found that the active sites of Mn3+ are generated by electron transfer from Mn2+ to the N of g-C3N4, and active N2 through the π back-donation process. This is evidenced by the experimental result that the NH3 yield rate of 5-Mn-CN significantly decreases from 15.2 μg h−1 mgcat−1 to 2.6 μg h−1 mgcat−1 after lowering the concentration of Mn3+. The concentration of Mn3+ is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N2 activation and provides insights into the transition metal-doped g-C3N4 as NRR catalysts.
{"title":"Effective Electrochemical Nitrogen Reduction through π Back-donation Process in Mn3+ of Mn-doped g-C3N4","authors":"Yijin Ma, Yinpeng Lu, Chang Li, Liangqing Hu, Hexin Zhang, Jing Feng","doi":"10.1007/s10562-024-04772-1","DOIUrl":"10.1007/s10562-024-04772-1","url":null,"abstract":"<div><p>Ammonia (NH<sub>3</sub>) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C<sub>3</sub>N<sub>4</sub> (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH<sub>3</sub> yield rate: 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup>, Faradaic efficiency: 7.1%) at -0.4 V (<i>vs. RHE</i>) than others. It is found that the active sites of Mn<sup>3+</sup> are generated by electron transfer from Mn<sup>2+</sup> to the N of g-C<sub>3</sub>N<sub>4,</sub> and active N<sub>2</sub> through the π back-donation process. This is evidenced by the experimental result that the NH<sub>3</sub> yield rate of 5-Mn-CN significantly decreases from 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> to 2.6 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> after lowering the concentration of Mn<sup>3+</sup>. The concentration of Mn<sup>3+</sup> is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N<sub>2</sub> activation and provides insights into the transition metal-doped g-C<sub>3</sub>N<sub>4</sub> as NRR catalysts.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5830 - 5837"},"PeriodicalIF":2.3,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1007/s10562-024-04769-w
María A. Vicerich, María A. Sánchez, Cristhian Fonseca Benítez, Vanina A. Mazzieri
The selection of an appropriate preparation method is crucial to enhance catalytic performance and optimize the resources used in catalyst synthesis. Achieving improvements in conversion rates, desired product yields are essential for increasing interest and competitiveness in the industrial sector. This study aims to analyze the influence of the preparation method of Rh(1%)-Sn(4%)/γ-Al2O3 catalysts on the selective hydrogenation of oleic acid to oleyl alcohol. Results from temperature-programmed reduction (TPR), cyclohexane dehydrogenation (DHC), and X-ray photoelectron spectroscopy (XPS) clearly demonstrate that incorporating sodium borohydride in the preparation process results in a stronger interaction between Rh and Sn. The degree of interaction between Rh and Sn is significantly influenced by the catalyst preparation and activation method, with a strong interaction promoting selectivity towards the formation of oleyl alcohol.
Graphical Abstract
选择合适的制备方法对于提高催化性能和优化催化剂合成过程中的资源使用至关重要。提高转化率和理想的产品收率对于增强工业领域的兴趣和竞争力至关重要。本研究旨在分析 Rh(1%)-Sn(4%)/γ-Al2O3 催化剂的制备方法对油酸选择性加氢制取油醇的影响。温度编程还原 (TPR)、环己烷脱氢 (DHC) 和 X 射线光电子能谱 (XPS) 的研究结果清楚地表明，在制备过程中加入硼氢化钠会增强 Rh 和 Sn 之间的相互作用。催化剂的制备和活化方法对 Rh 和 Sn 之间的相互作用程度有显著影响，强相互作用会提高生成油醇的选择性。
{"title":"Influence of the Activation Method of Rh-Sn-B/γ-Al2O3 Catalysts on the Selective Hydrogenation of Oleic Acid to Oleyl Alcohol","authors":"María A. Vicerich, María A. Sánchez, Cristhian Fonseca Benítez, Vanina A. Mazzieri","doi":"10.1007/s10562-024-04769-w","DOIUrl":"10.1007/s10562-024-04769-w","url":null,"abstract":"<div><p>The selection of an appropriate preparation method is crucial to enhance catalytic performance and optimize the resources used in catalyst synthesis. Achieving improvements in conversion rates, desired product yields are essential for increasing interest and competitiveness in the industrial sector. This study aims to analyze the influence of the preparation method of Rh(1%)-Sn(4%)/γ-Al<sub>2</sub>O<sub>3</sub> catalysts on the selective hydrogenation of oleic acid to oleyl alcohol. Results from temperature-programmed reduction (TPR), cyclohexane dehydrogenation (DHC), and X-ray photoelectron spectroscopy (XPS) clearly demonstrate that incorporating sodium borohydride in the preparation process results in a stronger interaction between Rh and Sn. The degree of interaction between Rh and Sn is significantly influenced by the catalyst preparation and activation method, with a strong interaction promoting selectivity towards the formation of oleyl alcohol.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5806 - 5816"},"PeriodicalIF":2.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.1007/s10562-024-04767-y
Malihe Hadadi, Alireza Habibi
Saccharification of cellulosic material is crucial before utilizing it as the feedstock of fermentation processes. This study focuses on developing of robust catalysts for enzymatic hydrolysis of paper waste. Cellulase enzyme was immobilized on Fe3O4 magnetic nanoparticles (MNPs) via multi-covalent bonds. Therefore, the attachments of MNPs were performed by three approaches (3-aminopropyl)triethoxysilane (APTES) (Method I), polyethyleneimine (PEI) (Method II), and both monolayer molybdenum disulfide and PEI (MoS2-PEI) (Method III). The biocatalysts were characterized using Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA). The immobilization yield and loading efficiency of cellulase were determined at 38.65% and 162 mg g−1 in Method I, 13.33% and 31 mg g−1 in Method II, and 14.38% and 33 mg g−1 in Method III. The specification of the biocatalysts was determined for the hydrolysis of filter paper, carboxymethylcellulose (CMC), microcrystalline cellulose, and cellobiose. The total cellulase activity was 2.77, 0.943, 1.38, and 2.02 µmolGlucose mgEnzyme−1 h−1for free-cellulase and the immobilized biocatalysts prepared by Method I, II, and III, respectively. The prepared biocatalyst in Method I maintained 54.54% of its original activity after five cycles, which was more robust than Method II (20.25%) and Method III (12.33%). Further studies were performed on the saccharification of paper waste. The results showed the biocatalyst obtained by Method II resulted in 5.8 folds of higher glucose than the free-cellulase. The highest glucose recovery of about 72.47% was achieved after 48 h using the immobilized biocatalyst prepared by Method II.
Graphical Abstract
在将纤维素材料用作发酵工艺的原料之前，对其进行糖化处理至关重要。本研究的重点是开发用于酶水解废纸的强效催化剂。纤维素酶通过多共价键固定在 Fe3O4 磁性纳米粒子（MNPs）上。因此，通过三种方法（3-氨丙基三乙氧基硅烷（APTES）（方法 I）、聚乙烯亚胺（PEI）（方法 II）以及单层二硫化钼和 PEI（MoS2-PEI）（方法 III））对 MNPs 进行了附着。利用傅立叶变换红外（FTIR）和热重分析（TGA）对生物催化剂进行了表征。经测定，方法 I 中纤维素酶的固定化产率和负载效率分别为 38.65% 和 162 mg g-1，方法 II 中分别为 13.33% 和 31 mg g-1，方法 III 中分别为 14.38% 和 33 mg g-1。测定了生物催化剂水解滤纸、羧甲基纤维素（CMC）、微晶纤维素和纤维生物糖的规格。用方法 I、II 和 III 制备的游离纤维素酶和固定化生物催化剂的总纤维素酶活性分别为 2.77、0.943、1.38 和 2.02 µmolGlucose mgEnzyme-1 h-1。方法 I 中制备的生物催化剂在五个周期后保持了 54.54% 的原始活性，比方法 II（20.25%）和方法 III（12.33%）更强。对废纸糖化进行了进一步研究。结果表明，用方法 II 获得的生物催化剂比游离纤维素酶产生的葡萄糖高 5.8 倍。采用方法 II 制备的固定化生物催化剂在 48 小时后的葡萄糖回收率最高，约为 72.47%。
{"title":"Development of Magnetic Immobilized Cellulase Biocatalysts for Saccharification of Paper Waste","authors":"Malihe Hadadi, Alireza Habibi","doi":"10.1007/s10562-024-04767-y","DOIUrl":"10.1007/s10562-024-04767-y","url":null,"abstract":"<div><p>Saccharification of cellulosic material is crucial before utilizing it as the feedstock of fermentation processes. This study focuses on developing of robust catalysts for enzymatic hydrolysis of paper waste. Cellulase enzyme was immobilized on Fe<sub>3</sub>O<sub>4</sub> magnetic nanoparticles (MNPs) via multi-covalent bonds. Therefore, the attachments of MNPs were performed by three approaches (3-aminopropyl)triethoxysilane (APTES) (Method I), polyethyleneimine (PEI) (Method II), and both monolayer molybdenum disulfide and PEI (MoS<sub>2</sub>-PEI) (Method III). The biocatalysts were characterized using Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA). The immobilization yield and loading efficiency of cellulase were determined at 38.65% and 162 mg g<sup>−1</sup> in Method I, 13.33% and 31 mg g<sup>−1</sup> in Method II, and 14.38% and 33 mg g<sup>−1</sup> in Method III. The specification of the biocatalysts was determined for the hydrolysis of filter paper, carboxymethylcellulose (CMC), microcrystalline cellulose, and cellobiose. The total cellulase activity was 2.77, 0.943, 1.38, and 2.02 µmol<sub>Glucose</sub> mg<sub>Enzyme</sub><sup>−1</sup> h<sup>−1</sup>for free-cellulase and the immobilized biocatalysts prepared by Method I, II, and III, respectively. The prepared biocatalyst in Method I maintained 54.54% of its original activity after five cycles, which was more robust than Method II (20.25%) and Method III (12.33%). Further studies were performed on the saccharification of paper waste. The results showed the biocatalyst obtained by Method II resulted in 5.8 folds of higher glucose than the free-cellulase. The highest glucose recovery of about 72.47% was achieved after 48 h using the immobilized biocatalyst prepared by Method II.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5791 - 5805"},"PeriodicalIF":2.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141547520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The modification of petroleum resin (PR) by catalytic hydrogenation is an upgrading technology for producing high-value-added hydrogenated petroleum resin (HPR) from of pyrolysis petroleum by-product. This research employed alumina supports with different pore size distributions to prepare supported Mo-Ni type catalysts and investigated their catalytic hydrogenation performance on C9 petroleum resin. Catalysts prepared with bimodal pore alumina (BPA) supports effectively overcome the limitations of internal diffusion and increase the quantity of active sites, thus increasing the catalytic activity for hydrogenation. The experimental results demonstrated that MoNi/BPA achieved a hydrogenation degree of 99.94% for HC9PR, with the hydrogenated product having a Pt–Co colour of 2.37 Hazen. After 140 h of reaction, the hydrogenation degree of HC9PR remained at 96.51%, and the Pt–Co colour value was lower than 40 Hazen. This investigation confirms that solving the mass transfer issues of petroleum resin molecules in the pores of supported catalysts is key to designing efficient hydrogenation catalysts for petroleum resin.
{"title":"Effect of Pore Structure on the Performance of Mo-Ni Catalysts for Petroleum Resin Hydrogenation","authors":"Tong Niu, Zhengyang Shi, Jinchang Sun, Qianwen Zhang","doi":"10.1007/s10562-024-04768-x","DOIUrl":"10.1007/s10562-024-04768-x","url":null,"abstract":"<div><p>The modification of petroleum resin (PR) by catalytic hydrogenation is an upgrading technology for producing high-value-added hydrogenated petroleum resin (HPR) from of pyrolysis petroleum by-product. This research employed alumina supports with different pore size distributions to prepare supported Mo-Ni type catalysts and investigated their catalytic hydrogenation performance on C<sub>9</sub> petroleum resin. Catalysts prepared with bimodal pore alumina (BPA) supports effectively overcome the limitations of internal diffusion and increase the quantity of active sites, thus increasing the catalytic activity for hydrogenation. The experimental results demonstrated that MoNi/BPA achieved a hydrogenation degree of 99.94% for HC<sub>9</sub>PR, with the hydrogenated product having a Pt–Co colour of 2.37 Hazen. After 140 h of reaction, the hydrogenation degree of HC<sub>9</sub>PR remained at 96.51%, and the Pt–Co colour value was lower than 40 Hazen. This investigation confirms that solving the mass transfer issues of petroleum resin molecules in the pores of supported catalysts is key to designing efficient hydrogenation catalysts for petroleum resin.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5781 - 5790"},"PeriodicalIF":2.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141547519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-03DOI: 10.1007/s10562-024-04747-2
Daomei Chen, Guo Xiao, Jian Tang, Lixia zhao, Sicong Li, Lingli Li, Bin Li, Tao Lei, Jiaqiang Wang
Developing efficient artificial proteases still remains a great challenge due to the high stability of peptide bonds. Nanozymes have attracted great attention for their high stability, low cost and inherent physicochemical properties, providing new opportunities to break through natural enzyme inherent limitations, but the intrinsic mimic proteases properties of nanomaterials were seldom explored. Herein, we describe for the first time that SBA-3 supported Cu2O (Cu2O/SBA-3) exhibited excellent protease-like activity to hydrolysis of bovine serum albumin (BSA) and casein under neutral conditions, which is even superior to natural proteases (trypsin) and most of the other protease mimics under identical conditions. It exhibited surprisingly high catalytic activity and possessed good stability. As the first example of protease mimics consist of metallic compounds and mesoporous materials, Cu2O/SBA-3 has many advantages, such as easy preparation and separation, high activity and stability, mild reaction conditions, which makes this catalytic system have multiple of potential applications in biological systems.
{"title":"Cu2O/SBA-3 Possess Intrinsic High Protease-Like Activity for Efficient Hydrolysis of Protein Under Physiological Conditions","authors":"Daomei Chen, Guo Xiao, Jian Tang, Lixia zhao, Sicong Li, Lingli Li, Bin Li, Tao Lei, Jiaqiang Wang","doi":"10.1007/s10562-024-04747-2","DOIUrl":"10.1007/s10562-024-04747-2","url":null,"abstract":"<div><p>Developing efficient artificial proteases still remains a great challenge due to the high stability of peptide bonds. Nanozymes have attracted great attention for their high stability, low cost and inherent physicochemical properties, providing new opportunities to break through natural enzyme inherent limitations, but the intrinsic mimic proteases properties of nanomaterials were seldom explored. Herein, we describe for the first time that SBA-3 supported Cu2O (Cu2O/SBA-3) exhibited excellent protease-like activity to hydrolysis of bovine serum albumin (BSA) and casein under neutral conditions, which is even superior to natural proteases (trypsin) and most of the other protease mimics under identical conditions. It exhibited surprisingly high catalytic activity and possessed good stability. As the first example of protease mimics consist of metallic compounds and mesoporous materials, Cu2O/SBA-3 has many advantages, such as easy preparation and separation, high activity and stability, mild reaction conditions, which makes this catalytic system have multiple of potential applications in biological systems.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5757 - 5768"},"PeriodicalIF":2.3,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141511516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-03DOI: 10.1007/s10562-024-04770-3
M. Sadegh Ramezani, Sadegh Safaei, Zahra Goodarzi, Mahsa Moradi
Herein, a modified synthesis method was presented and the effect of using an aqueous acetic acid solution in the process of synthesizing SQCOF was investigated. Adding a catalytic amount of aqueous solution of acetic acid as a co-catalyst has contributed to improving the quality of crystallinity. Effective parameters in the synthesis of SQCOF, including the concentration and volume of the co-catalyst and reaction solvent, were optimized. Then, the prepared SQCOF was used as a metal-free catalyst with Brønsted acid groups in the condensation reaction between 1,3-dicarbonyl compounds and primary amines. SQCOF was used under solvent-free conditions for the synthesis of enaminones at ambient temperature by mild manual grinding with a mortar and pestle and showed excellent catalytic performance in the above reaction. High performance and efficiency (62 to 96%), high TOF (833 to 1283 h−1), short reaction time, easy operation, minimizing the consumption of toxic organic solvents, absence of heavy metals in the framework and green conditions are the main advantages of this study. Also, SQCOF shows good chemical stability and recyclability (7 runs) and acts as an efficient catalyst in the synthesis of β-enaminones.
{"title":"Synthesis and Improving the Crystallinity of a Squaranine Covalent Organic Framework by Modifying the Preparation Method and Using it as a Green and Metal-Free Catalyst for the Synthesis of Enaminone","authors":"M. Sadegh Ramezani, Sadegh Safaei, Zahra Goodarzi, Mahsa Moradi","doi":"10.1007/s10562-024-04770-3","DOIUrl":"10.1007/s10562-024-04770-3","url":null,"abstract":"<div><p>Herein, a modified synthesis method was presented and the effect of using an aqueous acetic acid solution in the process of synthesizing SQCOF was investigated. Adding a catalytic amount of aqueous solution of acetic acid as a co-catalyst has contributed to improving the quality of crystallinity. Effective parameters in the synthesis of SQCOF, including the concentration and volume of the co-catalyst and reaction solvent, were optimized. Then, the prepared SQCOF was used as a metal-free catalyst with Brønsted acid groups in the condensation reaction between 1,3-dicarbonyl compounds and primary amines. SQCOF was used under solvent-free conditions for the synthesis of enaminones at ambient temperature by mild manual grinding with a mortar and pestle and showed excellent catalytic performance in the above reaction. High performance and efficiency (62 to 96%), high TOF (833 to 1283 h<sup>−1</sup>), short reaction time, easy operation, minimizing the consumption of toxic organic solvents, absence of heavy metals in the framework and green conditions are the main advantages of this study. Also, SQCOF shows good chemical stability and recyclability (7 runs) and acts as an efficient catalyst in the synthesis of <i>β</i>-enaminones.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5769 - 5780"},"PeriodicalIF":2.3,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141511551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-02DOI: 10.1007/s10562-024-04771-2
Yongjia Liang, Jianliang Zuo, Zhaohao Cai, Jing Lin, Zili Liu
The direct conversion of furfural (FA) from biomass to pentanediols (PeDs), including 1,2-PeD and 1,5-PeD, is important for replacing fossil resources and developing bio-based polyesters from renewable sources. However, achieving high selectivity for the C–O hydrogenation of the furan ring remains a significant challenge. In this study, we synthesized a series of trimetallic CuCoLa catalysts, using a coprecipitation method with various metal ratios. The reduced CuCoLa catalyst with a metal ratio of 1/3/1, exhibited the highest activity for the selective hydrogenolysis of FA to PeDs. Under optimal reaction conditions (160 °C, 4 MPa H2 for 9 h), CuCoLa(1/3/1)-R achieved yields of 21.7% for 1,2-PeD and 50.1% for 1,5-PeD. Furthermore, the catalyst remained stable after five cycles of FA conversion to PeDs. The high selectivity for PeDs is attributed to the synergistic interaction between Cu and Co and the appropriate number of basic surface sites.
{"title":"Highly Efficient CuCoLa Catalyst for the Direct Hydrogenation of Furfural to Pentanediols","authors":"Yongjia Liang, Jianliang Zuo, Zhaohao Cai, Jing Lin, Zili Liu","doi":"10.1007/s10562-024-04771-2","DOIUrl":"10.1007/s10562-024-04771-2","url":null,"abstract":"<div><p>The direct conversion of furfural (FA) from biomass to pentanediols (PeDs), including 1,2-PeD and 1,5-PeD, is important for replacing fossil resources and developing bio-based polyesters from renewable sources. However, achieving high selectivity for the C–O hydrogenation of the furan ring remains a significant challenge. In this study, we synthesized a series of trimetallic CuCoLa catalysts, using a coprecipitation method with various metal ratios. The reduced CuCoLa catalyst with a metal ratio of 1/3/1, exhibited the highest activity for the selective hydrogenolysis of FA to PeDs. Under optimal reaction conditions (160 °C, 4 MPa H<sub>2</sub> for 9 h), CuCoLa(1/3/1)-R achieved yields of 21.7% for 1,2-PeD and 50.1% for 1,5-PeD. Furthermore, the catalyst remained stable after five cycles of FA conversion to PeDs. The high selectivity for PeDs is attributed to the synergistic interaction between Cu and Co and the appropriate number of basic surface sites.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5745 - 5756"},"PeriodicalIF":2.3,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141511514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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