Catalysis Today最新文献_第10页

Sustainable hydrogenation of xylose to xylitol using nickel-alumina catalysts supported on hexagonal mesoporous silica in water vis-à-vis aqueous isopropanol as solvent 以六方介孔二氧化硅为载体的镍氧化铝催化剂在水中与异丙醇水溶液为溶剂进行木糖到木糖醇的可持续氢化反应

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-24 DOI: 10.1016/j.cattod.2024.115105

Sneha R. Shetty , Ganapati D. Yadav

Hydrogenation of xylose to xylitol is commercially attractive. The use of water as well as aqueous isopropanol as solvent using a novel robust catalyst was targeted in this work. This work showed that a nickel-alumina catalyst supported on hexagonal mesoporous silica (HMS) can effectively transform lignocellulose-derived xylose fraction to the value-added product, xylitol. HMS support was modified by simultaneous impregnating nickel (6 wt%) and alumina (4 wt%) which was subsequently oxidized. The catalyst was evaluated for its hydrogenation ability of xylose to xylitol. Identical reactions were carried out with HMS, alumina, Al/HMS and Ni/HMS to ascertain the activity of each moiety in the reaction. Before the reaction, the catalyst was reduced in a tubular reactor in the presence of hydrogen. Reaction parameters such as speed of agitation, type of precursor, metal loading, catalyst loading, solvent, concentration and temperature were studied and optimized. At 130℃ and 20 bar H₂, initial xylose concentration of 0.2 mmol/mL with water: isopropanol (1:1 v/v) mixture as solvent, conversion of xylose was found to be 98 % with a selectivity of 97 % towards xylitol. Comparison was also made with water alone as a solvent. A kinetic study of the reaction was performed. The transformation of xylose to xylitol using this novel catalyst is a green process since it entails substantially lower metal loading when compared to the conventional Raney nickel catalysts, it does not involve the use of noble metals such as Pt, Pd, Rh or Ru, and also does not suffer from the problem of metal leaching, making it superior to those catalysts reported yet.

将木糖加氢转化为木糖醇具有商业吸引力。本研究以水和异丙醇水溶液为溶剂，并使用新型强效催化剂为目标。这项研究表明，六方介孔二氧化硅（HMS）支撑的镍-氧化铝催化剂可以有效地将木质纤维素衍生的木糖部分转化为高附加值产品木糖醇。通过同时浸渍镍（6 wt%）和氧化铝（4 wt%）对 HMS 载体进行改性，然后对其进行氧化。对该催化剂将木糖氢化为木糖醇的能力进行了评估。用 HMS、氧化铝、Al/HMS 和 Ni/HMS 进行了相同的反应，以确定每个分子在反应中的活性。反应前，催化剂在有氢气存在的管式反应器中进行还原。对搅拌速度、前驱体类型、金属负载、催化剂负载、溶剂、浓度和温度等反应参数进行了研究和优化。在 130℃ 和 20 bar H2 条件下，以水：异丙醇（1:1 v/v）混合物为溶剂，木糖初始浓度为 0.2 mmol/mL，木糖转化率为 98%，对木糖醇的选择性为 97%。此外，还与单独用水作为溶剂进行了比较。对反应进行了动力学研究。使用这种新型催化剂将木糖转化为木糖醇是一种绿色工艺，因为与传统的雷尼镍催化剂相比，这种催化剂的金属负载量要低得多，而且不需要使用铂、钯、铑或钌等贵金属，也没有金属浸出的问题，因此比目前报道的催化剂更为优越。

{"title":"Sustainable hydrogenation of xylose to xylitol using nickel-alumina catalysts supported on hexagonal mesoporous silica in water vis-à-vis aqueous isopropanol as solvent","authors":"Sneha R. Shetty , Ganapati D. Yadav","doi":"10.1016/j.cattod.2024.115105","DOIUrl":"10.1016/j.cattod.2024.115105","url":null,"abstract":"<div><div>Hydrogenation of xylose to xylitol is commercially attractive. The use of water as well as aqueous isopropanol as solvent using a novel robust catalyst was targeted in this work. This work showed that a nickel-alumina catalyst supported on hexagonal mesoporous silica (HMS) can effectively transform lignocellulose-derived xylose fraction to the value-added product, xylitol. HMS support was modified by simultaneous impregnating nickel (6 wt%) and alumina (4 wt%) which was subsequently oxidized. The catalyst was evaluated for its hydrogenation ability of xylose to xylitol. Identical reactions were carried out with HMS, alumina, Al/HMS and Ni/HMS to ascertain the activity of each moiety in the reaction. Before the reaction, the catalyst was reduced in a tubular reactor in the presence of hydrogen. Reaction parameters such as speed of agitation, type of precursor, metal loading, catalyst loading, solvent, concentration and temperature were studied and optimized. At 130℃ and 20 bar H2, initial xylose concentration of 0.2 mmol/mL with water: isopropanol (1:1 v/v) mixture as solvent, conversion of xylose was found to be 98 % with a selectivity of 97 % towards xylitol. Comparison was also made with water alone as a solvent. A kinetic study of the reaction was performed. The transformation of xylose to xylitol using this novel catalyst is a green process since it entails substantially lower metal loading when compared to the conventional Raney nickel catalysts, it does not involve the use of noble metals such as Pt, Pd, Rh or Ru, and also does not suffer from the problem of metal leaching, making it superior to those catalysts reported yet.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"446 ","pages":"Article 115105"},"PeriodicalIF":5.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142658793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of manganese oxides supported on zeolite Y on catalytic oxidation of benzene by ozone 沸石 Y 上支撑的锰氧化物对臭氧催化氧化苯的影响

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-24 DOI: 10.1016/j.cattod.2024.115104

Xuerui Zheng , Hisahiro Einaga

Manganese oxide catalysts with different structures and loading levels were supported on zeolite Y catalysts using a dry impregnation method for the oxidation of low concentrations of benzene with ozone. X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) studies revealed that manganese oxide was highly dispersed on the zeolite in a low oxidation state for those prepared with the acetate precursor, and highly oxidized and aggregated manganese oxide for those prepared with the nitrate precursor. In the reaction at 70 ℃, the benzene oxidation rate, CO₂ selectivity, and ozone/benzene decomposition ratio were independent of the manganese loading, manganese precursor, and zeolite Y porosity. These catalytic properties were found to be less dependent on the manganese oxide structure. A slight increase in the reaction temperature enhanced both the catalytic activity and the catalyst performance, while the presence of water vapor had no significant impact. The XAFS analysis of the spent catalysts indicated that during the benzene decomposition reaction, the structure of the manganese oxide loaded on the catalyst was altered, and its oxidation state was uniformly reduced.

采用干法浸渍法在沸石 Y 催化剂上支撑了不同结构和负载水平的氧化锰催化剂，用于用臭氧氧化低浓度苯。X 射线衍射（XRD）和 X 射线吸收精细结构（XAFS）研究表明，用醋酸盐前驱体制备的氧化锰以低氧化态高度分散在沸石上，而用硝酸盐前驱体制备的氧化锰则高度氧化和聚集。在 70 ℃ 的反应中，苯氧化率、二氧化碳选择性和臭氧/苯分解率与锰负载量、锰前体和沸石 Y 的孔隙率无关。这些催化特性对氧化锰结构的依赖性较小。反应温度略微升高可提高催化活性和催化剂性能，而水蒸气的存在则无明显影响。对废催化剂的 XAFS 分析表明，在苯分解反应过程中，催化剂上负载的氧化锰结构发生了改变，其氧化态均匀降低。

{"title":"Effect of manganese oxides supported on zeolite Y on catalytic oxidation of benzene by ozone","authors":"Xuerui Zheng , Hisahiro Einaga","doi":"10.1016/j.cattod.2024.115104","DOIUrl":"10.1016/j.cattod.2024.115104","url":null,"abstract":"<div><div>Manganese oxide catalysts with different structures and loading levels were supported on zeolite Y catalysts using a dry impregnation method for the oxidation of low concentrations of benzene with ozone. X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) studies revealed that manganese oxide was highly dispersed on the zeolite in a low oxidation state for those prepared with the acetate precursor, and highly oxidized and aggregated manganese oxide for those prepared with the nitrate precursor. In the reaction at 70 ℃, the benzene oxidation rate, CO2 selectivity, and ozone/benzene decomposition ratio were independent of the manganese loading, manganese precursor, and zeolite Y porosity. These catalytic properties were found to be less dependent on the manganese oxide structure. A slight increase in the reaction temperature enhanced both the catalytic activity and the catalyst performance, while the presence of water vapor had no significant impact. The XAFS analysis of the spent catalysts indicated that during the benzene decomposition reaction, the structure of the manganese oxide loaded on the catalyst was altered, and its oxidation state was uniformly reduced.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"446 ","pages":"Article 115104"},"PeriodicalIF":5.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ni/Al2O3 promoted by CeO2, CeO2-La2O3, and CeO2-ZrO2 supported on cordierite monoliths for methane steam reforming 以堇青石整体柱为支撑的 CeO2、CeO2-La2O3 和 CeO2-ZrO2 促进 Ni/Al2O3 用于甲烷蒸汽转化

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-24 DOI: 10.1016/j.cattod.2024.115107

Victória Gonçalves F Pereira , Ana Serrano-Lotina , Raquel Portela , Miguel A. Bañares , Clarissa Perdomo Rodrigues , Fabio Souza Toniolo

Promotion of Ni-based catalysts supported on cordierite monoliths was investigated for methane steam reforming. First, cordierite was coated by ɣ-Al₂O_3, and then the catalyst components were deposited by successive wet impregnation, obtaining: NiAl/cordierite; NiCeAl/cordierite; NiCeLaAl/cordierite and NiCeZrAl/cordierite. The monolithic catalysts were characterized by adherence test, Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDX), N₂ physisorption, Temperature-Programmed Reduction (TPR), CO chemisorption, as well as by in situ and operando Raman spectroscopy. The catalyst layer showed very good adherence and distribution of the components over the cordierite surface. The catalysts presented high activity between 600 and 800 °C at a H₂O/CH₄ molar ratio=1.5, except for NiCeAl/cordierite, which obtained lower methane conversion, associated with its lower nickel dispersion. The catalysts showed high stability under extreme conditions for carbon deposition (600 °C and H₂O/CH₄=1), over 90 h on stream. Raman spectroscopy revealed the presence of oxygen vacancies, which may be increased during ceria reduction, highlighting the potential of these catalysts to enhance the resistance to deactivation by carbon deposition in long-term tests.

研究了堇青石整体支撑的镍基催化剂对甲烷蒸汽转化的促进作用。首先用ɣ-Al2O3 对堇青石进行包覆，然后通过连续湿法浸渍沉积催化剂组分，得到了NiAl/堇青石、NiCeAl/堇青石、NiCeLaAl/堇青石和 NiCeZrAl/堇青石。通过附着力测试、扫描电子显微镜与能量色散 X 射线光谱（SEM-EDX）、N2 物理吸附、温度编程还原（TPR）、CO 化学吸附以及原位和操作拉曼光谱，对整体催化剂进行了表征。催化剂层在堇青石表面显示出非常好的附着性和组分分布。在 H2O/CH4 摩尔比=1.5 的条件下，催化剂在 600 至 800 °C 之间表现出较高的活性，但 NiCeAl/cordierite 除外，其甲烷转化率较低，这与其镍分散度较低有关。在碳沉积的极端条件下（600 °C，H2O/CH4=1），催化剂在90小时内显示出很高的稳定性。拉曼光谱显示存在氧空位，这可能在铈还原过程中增加，突出了这些催化剂在长期测试中提高抗碳沉积失活能力的潜力。

{"title":"Ni/Al2O3 promoted by CeO2, CeO2-La2O3, and CeO2-ZrO2 supported on cordierite monoliths for methane steam reforming","authors":"Victória Gonçalves F Pereira , Ana Serrano-Lotina , Raquel Portela , Miguel A. Bañares , Clarissa Perdomo Rodrigues , Fabio Souza Toniolo","doi":"10.1016/j.cattod.2024.115107","DOIUrl":"10.1016/j.cattod.2024.115107","url":null,"abstract":"<div><div>Promotion of Ni-based catalysts supported on cordierite monoliths was investigated for methane steam reforming. First, cordierite was coated by ɣ-Al2O3, and then the catalyst components were deposited by successive wet impregnation, obtaining: NiAl/cordierite; NiCeAl/cordierite; NiCeLaAl/cordierite and NiCeZrAl/cordierite. The monolithic catalysts were characterized by adherence test, Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDX), N2 physisorption, Temperature-Programmed Reduction (TPR), CO chemisorption, as well as by in situ and operando Raman spectroscopy. The catalyst layer showed very good adherence and distribution of the components over the cordierite surface. The catalysts presented high activity between 600 and 800 °C at a H2O/CH4 molar ratio=1.5, except for NiCeAl/cordierite, which obtained lower methane conversion, associated with its lower nickel dispersion. The catalysts showed high stability under extreme conditions for carbon deposition (600 °C and H2O/CH4=1), over 90 h on stream. Raman spectroscopy revealed the presence of oxygen vacancies, which may be increased during ceria reduction, highlighting the potential of these catalysts to enhance the resistance to deactivation by carbon deposition in long-term tests.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115107"},"PeriodicalIF":5.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selectivity modulation in Fischer-Tropsch synthesis through reducibility control of cobalt-species containing HMS framework 通过控制含钴种 HMS 框架的还原性调节费托合成中的选择性

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-23 DOI: 10.1016/j.cattod.2024.115110

T.A. Zepeda

Here reports the modulation of selectivity in Fischer-Tropsch synthesis through the control of cobalt reducibility within a hexagonal mesoporous silica (HMS) framework. Cobalt loading, varied from 3 % to 12.5 wt%, generated different surface and bulk cobalt species that interact variably with the support, significantly influencing their reducibility and the resultant catalytic behavior. This variation significantly affected the reducibility of the cobalt species, influencing on the catalytic behavior. The control of reducibility and stability of Co species is contingent on the cobalt loading. Higher cobalt content enhances the reducibility of Co species, shifting product selectivity from long-chain hydrocarbons to lighter olefins and oxygenates. At a TOS of 4 h, the active phase predominantly involves metallic Co species, while CO₂ and oxygenates formation is closely linked to the pair Co⁰-Co²⁺ active phase. After a TOS of 120 h, samples with higher cobalt content (6.1–15.8 % wt.) exhibited notable deactivation and changes in selectivity and hydrocarbon distribution. These changes were associated with the formation of a Co₂C phase, which inhibits methane formation and chain growth while enhancing the production of lower olefins and oxygenates through a synergistic interaction at the Co⁰ and Co₂C interface, also improves the WGS reaction, thereby increasing CO₂ selectivity.

本文报告了通过控制六方介孔二氧化硅（HMS）框架内的钴还原性来调节费托合成中的选择性。钴的负载量从 3% 到 12.5 wt% 不等，产生了不同的表面和块体钴物种，这些钴物种与支持物的相互作用各不相同，极大地影响了它们的还原性和由此产生的催化行为。这种变化极大地影响了钴物种的还原性，从而影响了催化行为。钴物种的还原性和稳定性取决于钴的负载量。钴含量越高，钴物种的还原性越强，产品选择性从长链烃类转向较轻的烯烃和含氧化合物。在 4 小时的总反应时间内，活性相主要涉及金属 Co 物种，而 CO2 和含氧化合物的形成则与一对 Co0-Co2+ 活性相密切相关。在 120 小时的 TOS 之后，钴含量较高的样品（6.1-15.8% wt.）表现出明显的失活以及选择性和碳氢化合物分布的变化。这些变化与 Co2C 相的形成有关，Co2C 相通过 Co0 和 Co2C 界面的协同作用，抑制了甲烷的形成和链增长，同时提高了低级烯烃和含氧化合物的产量，还改善了 WGS 反应，从而提高了二氧化碳的选择性。

{"title":"Selectivity modulation in Fischer-Tropsch synthesis through reducibility control of cobalt-species containing HMS framework","authors":"T.A. Zepeda","doi":"10.1016/j.cattod.2024.115110","DOIUrl":"10.1016/j.cattod.2024.115110","url":null,"abstract":"<div><div>Here reports the modulation of selectivity in Fischer-Tropsch synthesis through the control of cobalt reducibility within a hexagonal mesoporous silica (HMS) framework. Cobalt loading, varied from 3 % to 12.5 wt%, generated different surface and bulk cobalt species that interact variably with the support, significantly influencing their reducibility and the resultant catalytic behavior. This variation significantly affected the reducibility of the cobalt species, influencing on the catalytic behavior. The control of reducibility and stability of Co species is contingent on the cobalt loading. Higher cobalt content enhances the reducibility of Co species, shifting product selectivity from long-chain hydrocarbons to lighter olefins and oxygenates. At a TOS of 4 h, the active phase predominantly involves metallic Co species, while CO2 and oxygenates formation is closely linked to the pair Co0-Co2+ active phase. After a TOS of 120 h, samples with higher cobalt content (6.1–15.8 % wt.) exhibited notable deactivation and changes in selectivity and hydrocarbon distribution. These changes were associated with the formation of a Co2C phase, which inhibits methane formation and chain growth while enhancing the production of lower olefins and oxygenates through a synergistic interaction at the Co0 and Co2C interface, also improves the WGS reaction, thereby increasing CO2 selectivity.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115110"},"PeriodicalIF":5.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531573","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chemistry in rechargeable zinc-air battery: A mechanistic overview 可充电锌-空气电池中的化学成分：机理概述

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-23 DOI: 10.1016/j.cattod.2024.115108

Arkaj Singh, Ravinder Sharma, Akriti Gautam, Bhavnish Kumar, Sneha Mittal, Aditi Halder

The progress in civilization can be related to the development of newer technological development and associated energy demand to run those systems. The personalized healthcare systems, the depletion of conventional fossil fuel reserve led us to think about alternative energy storage devices. Thus, it is important to develop energy storage materials with the property of good mechanical strength and stability for longer hours. Zn-air batteries (ZAB) show the promises to be an alternative of Li-air batteries for this purpose. ZABs can fulfill our need of stringent requirements such as high energy density, cost-effectiveness and it is safer as compared to Li-ion batteries. The stability of zinc in aqueous and air environments makes ZAB technology more reliable and effective for small to large-scale flexible electronics. To further enhance its efficiency, different scientific materials and methods have been developed over decades, of which this review provides detailed insight into the parameters and mechanisms related to the key components of the ZAB for enhancing the performance of ZAB. We summarized the working mechanism of overall reversible-ZABs and then independently we explained the mechanism and problems associated with cathode, anode, and electrolyte, followed by the current breakthrough related to each. Aspects such as role of optimal e_g occupancy in bifunctional activity, inhibition of zinc dendrite, and gel polymer electrolytes with enhanced conductivity and strength are specifically highlighted. To facilitate a broad discussion among different research communities, important scientific hurdles and their potential solution related to R-ZABs are also summarized.

文明的进步与更新技术的发展以及运行这些系统的相关能源需求有关。个性化的医疗保健系统、传统化石燃料储备的枯竭促使我们思考替代能源存储设备。因此，开发具有良好机械强度和长时间稳定性的储能材料非常重要。为此，锌空气电池（ZAB）有望成为锂空气电池的替代品。与锂离子电池相比，锌空气电池能满足我们对高能量密度、成本效益和安全性的严格要求。锌在水和空气环境中的稳定性使 ZAB 技术在小型到大型柔性电子产品中更加可靠和有效。为了进一步提高其效率，几十年来人们开发了不同的科学材料和方法，本综述将详细介绍与 ZAB 关键部件相关的参数和机制，以提高 ZAB 的性能。我们总结了整体可逆ZAB的工作机理，然后分别解释了阴极、阳极和电解质的相关机理和问题，随后介绍了目前与每个部件相关的突破。我们还特别强调了最佳eg 占有率在双功能活性中的作用、锌枝晶抑制以及具有更强导电性和强度的凝胶聚合物电解质等方面的问题。为了便于不同研究界进行广泛讨论，还总结了与 R-ZAB 有关的重要科学障碍及其潜在解决方案。

{"title":"Chemistry in rechargeable zinc-air battery: A mechanistic overview","authors":"Arkaj Singh, Ravinder Sharma, Akriti Gautam, Bhavnish Kumar, Sneha Mittal, Aditi Halder","doi":"10.1016/j.cattod.2024.115108","DOIUrl":"10.1016/j.cattod.2024.115108","url":null,"abstract":"<div><div>The progress in civilization can be related to the development of newer technological development and associated energy demand to run those systems. The personalized healthcare systems, the depletion of conventional fossil fuel reserve led us to think about alternative energy storage devices. Thus, it is important to develop energy storage materials with the property of good mechanical strength and stability for longer hours. Zn-air batteries (ZAB) show the promises to be an alternative of Li-air batteries for this purpose. ZABs can fulfill our need of stringent requirements such as high energy density, cost-effectiveness and it is safer as compared to Li-ion batteries. The stability of zinc in aqueous and air environments makes ZAB technology more reliable and effective for small to large-scale flexible electronics. To further enhance its efficiency, different scientific materials and methods have been developed over decades, of which this review provides detailed insight into the parameters and mechanisms related to the key components of the ZAB for enhancing the performance of ZAB. We summarized the working mechanism of overall reversible-ZABs and then independently we explained the mechanism and problems associated with cathode, anode, and electrolyte, followed by the current breakthrough related to each. Aspects such as role of optimal eg occupancy in bifunctional activity, inhibition of zinc dendrite, and gel polymer electrolytes with enhanced conductivity and strength are specifically highlighted. To facilitate a broad discussion among different research communities, important scientific hurdles and their potential solution related to R-ZABs are also summarized.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115108"},"PeriodicalIF":5.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring reactivity of small Ag/Pt bimetallic cluster for ORR: A comprehensive study using density functional theory approach 调整小型 Ag/Pt 双金属团簇在 ORR 中的反应活性：利用密度泛函理论方法进行的综合研究

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-22 DOI: 10.1016/j.cattod.2024.115102

Sandeep Nigam , Chiranjib Majumder

Bimetallic clusters, as the name suggests, are known to act as bifunctional catalyst. Therefore, it is possible to tune the composition of the catalyst to achieve the best performance for a specific reaction. In the first part of this work, we explore the geometric and electronic structures of various Ag-Pt bimetallic clusters and find the right composition for ORR, one of the most sought-after reactions in the field of energy materials. We have considered Ag-Pt bimetallic clusters in both free and on Al₂O₃(0001) support. The results reveal that the equilibrium structures of the bimetallic Ag_nPt_m (n+m ≤ 12 atoms) clusters are governed by a balance of competing interactions (Pt-Pt vs Ag-Pt vs cluster-support interactions). Whilst the isolated decamer cluster with 5:5 or 6:4 composition (Ag₆Pt₄ and Ag₅Pt₅) shows atomically segregated structures, Ag rich clusters (Ag₉Pt_1–3) prefer to form core-shell pattern where Pt forms the core surrounded by Ag atoms. In general, these clusters adopt pseudo-planar structure on alumina support following the surface template. Analysis of the electronic structure shows that Al₂O₃ surface induces significant broadening in the energy states of the bimetallic cluster, which in turn facilitates higher mixing between d-states of the Ag and Pt in the complex. Finally, the d-band centre descriptor model has been utilized to underscore the chemical reactivity of these bimetallic clusters. Remarkably, the Ag₆Pt₄@Al₂O₃ cluster with d-band centre at −2.68 eV is found to be in “just right” zone for ORR. This is further corroborated by the reduction (∼ 25 %) in oxidation reaction enthalpy of the Ag₆Pt₄@Al₂O₃ than standard Pt(111) catalytic surface.

双金属团簇，顾名思义，具有双功能催化剂的作用。因此，可以通过调节催化剂的组成来实现特定反应的最佳性能。在这项工作的第一部分，我们探索了各种银铂双金属团簇的几何和电子结构，并找到了用于 ORR（能源材料领域最热门的反应之一）的合适成分。我们研究了游离和Al2O3(0001)支撑下的银铂双金属团簇。研究结果表明，双金属 AgnPtm（n+m ≤ 12 个原子）团簇的平衡结构受相互竞争的相互作用（Pt-Pt 与 Ag-Pt 之间的相互作用以及团簇与支撑物之间的相互作用）的影响。组成比例为 5:5 或 6:4 的孤立十聚体团簇（Ag6Pt4 和 Ag5Pt5）显示出原子隔离结构，而富含 Ag 的团簇（Ag9Pt1-3）则倾向于形成核壳模式，其中铂形成核心，周围环绕着 Ag 原子。一般来说，这些团簇在氧化铝载体上按照表面模板采用伪平面结构。对电子结构的分析表明，Al2O3 表面使双金属团簇的能态显著拓宽，这反过来又促进了复合物中银和铂的 d 态之间的混合。最后，利用 d 带中心描述模型强调了这些双金属簇的化学反应活性。值得注意的是，发现 d 波段中心在 -2.68 eV 的 Ag6Pt4@Al2O3 簇处于 ORR 的 "恰到好处 "区域。与标准铂（111）催化表面相比，Ag6Pt4@Al2O3 的氧化反应焓降低了 25%，进一步证实了这一点。

{"title":"Tailoring reactivity of small Ag/Pt bimetallic cluster for ORR: A comprehensive study using density functional theory approach","authors":"Sandeep Nigam , Chiranjib Majumder","doi":"10.1016/j.cattod.2024.115102","DOIUrl":"10.1016/j.cattod.2024.115102","url":null,"abstract":"<div><div>Bimetallic clusters, as the name suggests, are known to act as bifunctional catalyst. Therefore, it is possible to tune the composition of the catalyst to achieve the best performance for a specific reaction. In the first part of this work, we explore the geometric and electronic structures of various Ag-Pt bimetallic clusters and find the right composition for ORR, one of the most sought-after reactions in the field of energy materials. We have considered Ag-Pt bimetallic clusters in both free and on Al2O3(0001) support. The results reveal that the equilibrium structures of the bimetallic AgnPtm (n+m ≤ 12 atoms) clusters are governed by a balance of competing interactions (Pt-Pt vs Ag-Pt vs cluster-support interactions). Whilst the isolated decamer cluster with 5:5 or 6:4 composition (Ag6Pt4 and Ag5Pt5) shows atomically segregated structures, Ag rich clusters (Ag9Pt1–3) prefer to form core-shell pattern where Pt forms the core surrounded by Ag atoms. In general, these clusters adopt pseudo-planar structure on alumina support following the surface template. Analysis of the electronic structure shows that Al2O3 surface induces significant broadening in the energy states of the bimetallic cluster, which in turn facilitates higher mixing between d-states of the Ag and Pt in the complex. Finally, the d-band centre descriptor model has been utilized to underscore the chemical reactivity of these bimetallic clusters. Remarkably, the Ag6Pt4@Al2O3 cluster with d-band centre at −2.68 eV is found to be in “just right” zone for ORR. This is further corroborated by the reduction (∼ 25 %) in oxidation reaction enthalpy of the Ag6Pt4@Al2O3 than standard Pt(111) catalytic surface.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115102"},"PeriodicalIF":5.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Green synthesis of niobium (V) oxide nanoparticles using pecan nutshell (Carya illinoinensis) and evaluation of its antioxidant activity 利用山核桃果壳（Carya illinoinensis）绿色合成纳米氧化铌（V）颗粒并评估其抗氧化活性

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-21 DOI: 10.1016/j.cattod.2024.115106

Luís Fernando Wentz Brum , Maurício Dalla Costa Rodrigues da Silva , Cristiane dos Santos , Giovani Pavoski , Denise Crocce Romano Espinosa , William Leonardo da Silva

Niobium is a metal that has been attracting great interest in producing high-technology materials, in which niobium oxide nanoparticles (Nb₂O₅-NPs) are inserted. In this context, the present study aims to develop and characterize structurally and morphologically niobium (V) oxide nanoparticles (Nb₂O₅-NPs) by the green synthesis method from pecan nutshell (C. illinoinensis) extract. Nb₂O₅-NPs were characterized by Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and N₂ porosimetry (BET/BJH method). The antioxidant potential of the pecan nutshell extract was determined for the quantification of phenolic compounds and flavonoids. The XRD diffractogram showed that the Nb₂O₅-NPs presented a semicrystalline structure with the presence of the pseudohexagonal phase of Nb₂O₅. The ATR-FTIR spectrum confirmed the presence of a band vibration of the Nb-O at 600 cm⁻¹. The Nb₂O₅-NPs presented spherical morphology according to the SEM micrography with a specific surface area of 1.72 m² g⁻¹ and 36.31 nm pore diameter (isotherm type III) by the N₂ porosimetry. The pecan nutshell extract showed the presence of polyphenols (336.8 mgAG mL⁻¹) and flavonoids (200.1 mgCt mL⁻¹), demonstrating the high potential to act as a bioreducing and stabilizing agent for the green synthesis of Nb₂O₅-NPs. Therefore, the green synthesis of Nb₂O₅-NPs is feasible with potential application in different fields.

铌是一种金属，在生产高科技材料方面一直备受关注，铌氧化物纳米颗粒（Nb2O5-NPs）就是其中的一种。在此背景下，本研究旨在利用山核桃果壳（C. illinoinensis）提取物的绿色合成方法，开发氧化铌（V）纳米颗粒（Nb2O5-NPs）并确定其结构和形态特征。通过衰减全反射傅立叶变换红外光谱（ATR-FTIR）、扫描电子显微镜（SEM）、X 射线衍射（XRD）和 N2 孔隙比色法（BET/BJH 法）对 Nb2O5-NPs 进行了表征。山核桃果壳提取物的抗氧化潜力是通过酚类化合物和类黄酮的定量来确定的。XRD 衍射图显示，Nb2O5-NPs 呈半晶体结构，存在 Nb2O5 的假六方相。ATR-FTIR 光谱证实在 600 cm-1 处存在 Nb-O 的带振动。根据扫描电子显微镜显微照片，Nb2O5-NPs 呈球形，比表面积为 1.72 m2 g-1，根据 N2 孔隙度测定法，孔径为 36.31 nm（等温线类型 III）。山核桃果壳提取物中含有多酚（336.8 mgAG mL-1）和黄酮类化合物（200.1 mgCt mL-1），这表明山核桃果壳提取物在绿色合成 Nb2O5-NPs 的生物还原剂和稳定剂方面具有很高的潜力。因此，Nb2O5-NPs 的绿色合成是可行的，有望应用于不同领域。

{"title":"Green synthesis of niobium (V) oxide nanoparticles using pecan nutshell (Carya illinoinensis) and evaluation of its antioxidant activity","authors":"Luís Fernando Wentz Brum , Maurício Dalla Costa Rodrigues da Silva , Cristiane dos Santos , Giovani Pavoski , Denise Crocce Romano Espinosa , William Leonardo da Silva","doi":"10.1016/j.cattod.2024.115106","DOIUrl":"10.1016/j.cattod.2024.115106","url":null,"abstract":"<div><div>Niobium is a metal that has been attracting great interest in producing high-technology materials, in which niobium oxide nanoparticles (Nb2O5-NPs) are inserted. In this context, the present study aims to develop and characterize structurally and morphologically niobium (V) oxide nanoparticles (Nb2O5-NPs) by the green synthesis method from pecan nutshell (C. illinoinensis) extract. Nb2O5-NPs were characterized by Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and N2 porosimetry (BET/BJH method). The antioxidant potential of the pecan nutshell extract was determined for the quantification of phenolic compounds and flavonoids. The XRD diffractogram showed that the Nb2O5-NPs presented a semicrystalline structure with the presence of the pseudohexagonal phase of Nb2O5. The ATR-FTIR spectrum confirmed the presence of a band vibration of the Nb-O at 600 cm−1. The Nb2O5-NPs presented spherical morphology according to the SEM micrography with a specific surface area of 1.72 m2 g−1 and 36.31 nm pore diameter (isotherm type III) by the N2 porosimetry. The pecan nutshell extract showed the presence of polyphenols (336.8 mgAG mL−1) and flavonoids (200.1 mgCt mL−1), demonstrating the high potential to act as a bioreducing and stabilizing agent for the green synthesis of Nb2O5-NPs. Therefore, the green synthesis of Nb2O5-NPs is feasible with potential application in different fields.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115106"},"PeriodicalIF":5.2,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced photo/electrocatalytic efficiency of Zn-decorated TiO2 nanostructures for sustainable hydrogen evolution 提高锌装饰 TiO2 纳米结构的光催化/电催化效率，实现可持续氢气进化

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-20 DOI: 10.1016/j.cattod.2024.115103

Mohd Fazil , Jahangeer Ahmed , Tokeer Ahmad

Monophasic 1, 2.5, and 5 % Zn-decorated TiO₂ nanocatalysts have been fabricated by environmentally benign hydrothermal synthesis by avoiding expensive chemicals. As- prepared nanostructures have been investigated utilizing various sophisticated instruments like XRD, scanning and transmission electron microscopy, EDAX, Raman, optoelectronics as well as BET Surface Area studies. 2.5 % Zn- decorated TiO₂ was found to have superior photocatalytic performance, exhibiting an H₂ formation of 25.55 mmol

g_{cat}^{- 1}

in 8 hours and average H₂ generation of 3.15 mmol

g_{cat}^{- 1}

h⁻¹ at 170 W light intensity. Additionally, electrochemical investigations showed that 5 % and 2.5 % Zn-doped TiO₂ had a higher cathodic and anodic current density of 10 mA/cm² at −0.95, indicating that it has a higher HER catalytic activity, respectively. The synergistic impact of pristine TiO₂ and Zn-incorporated TiO₂ nanocatalysts is responsible for the increased kinetics of H₂ evolution, as it increases the separation and transfer of photo-charged (e^-/h⁺ pair) carriers and decreases redox potential for HER.

单相 1%、2.5% 和 5% 镀锌二氧化钛纳米催化剂是通过无害环境的水热合成法制造的，避免了昂贵的化学品。制备的纳米结构利用各种精密仪器进行了研究，如 XRD、扫描和透射电子显微镜、EDAX、拉曼、光电子学以及 BET 表面积研究。研究发现，2.5 % Zn- 装饰的二氧化钛具有优异的光催化性能，在 170 W 光强下，8 小时内可生成 25.55 mmolgcat-1 的 H2，平均 H2 生成量为 3.15 mmolgcat-1h-1。此外，电化学研究表明，掺杂 5 % 和 2.5 % Zn 的 TiO2 在-0.95 时的阴极和阳极电流密度分别为 10 mA/cm2，表明其具有更高的 HER 催化活性。原始 TiO2 和掺杂 Zn 的 TiO2 纳米催化剂的协同作用是提高 H2 演化动力学的原因，因为它增加了光带电（e-/h+ 对）载流子的分离和转移，降低了 HER 的氧化还原电位。

{"title":"Enhanced photo/electrocatalytic efficiency of Zn-decorated TiO2 nanostructures for sustainable hydrogen evolution","authors":"Mohd Fazil , Jahangeer Ahmed , Tokeer Ahmad","doi":"10.1016/j.cattod.2024.115103","DOIUrl":"10.1016/j.cattod.2024.115103","url":null,"abstract":"<div><div>Monophasic 1, 2.5, and 5 % Zn-decorated TiO2 nanocatalysts have been fabricated by environmentally benign hydrothermal synthesis by avoiding expensive chemicals. As- prepared nanostructures have been investigated utilizing various sophisticated instruments like XRD, scanning and transmission electron microscopy, EDAX, Raman, optoelectronics as well as BET Surface Area studies. 2.5 % Zn- decorated TiO2 was found to have superior photocatalytic performance, exhibiting an H2 formation of 25.55 mmol<math><msubsup><mrow><mi>g</mi></mrow><mrow><mi>cat</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup></math> in 8 hours and average H2 generation of 3.15 mmol<math><msubsup><mrow><mi>g</mi></mrow><mrow><mi>cat</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup></math>h−1 at 170 W light intensity. Additionally, electrochemical investigations showed that 5 % and 2.5 % Zn-doped TiO2 had a higher cathodic and anodic current density of 10 mA/cm2 at −0.95, indicating that it has a higher HER catalytic activity, respectively. The synergistic impact of pristine TiO2 and Zn-incorporated TiO2 nanocatalysts is responsible for the increased kinetics of H2 evolution, as it increases the separation and transfer of photo-charged (e-/h+ pair) carriers and decreases redox potential for HER.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115103"},"PeriodicalIF":5.2,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Layered double hydroxides for industrial wastewater remediation: A review 用于工业废水修复的层状双氢氧化物：综述

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-19 DOI: 10.1016/j.cattod.2024.115101

Sudarshan Sarkar, Chandan Upadhyay

Tanneries and textile industries significantly impact aquatic ecosystems through the discharge of effluents containing heavy metals, dyes, and metal-resistant bacterial pathogens. This review examines the potential of layered double hydroxides (LDHs) for addressing these environmental challenges. It offers a comprehensive analysis of LDH morphology, synthesis techniques, and performance in wastewater remediation. LDHs are ionic lamellar hydroxides, containing two different metal cations in the main layers and anionic species in the interlayer, have attracted substantial research interest due to their ease of synthesis and unique properties. This review distinguishes itself by correlating various synthesis methods for LDHs directly with their efficacy in wastewater remediation, offering insights not typically covered in other reviews. Furthermore, the review explores the critical role of interlayer anions, such as carbonate and sulfate, in determining its influence in the structural, chemical, and physical properties of LDHs. It also addresses how modifications with graphitic carbon nitride (gC₃N₄) and graphene-based materials enhance LDH’s performance by increasing surface area, delaying charge recombination, and improving adsorption and photocatalytic activity. he review evaluates the impact of these factors on the removal of pollutants from wastewater and provides an in-depth discussion of the mechanisms involved in pollutant removal, including adsorption, ion exchange, and photocatalysis. It also highlights the antibacterial properties of LDHs, particularly when combined with advanced materials, demonstrating their potential antimicrobial efficacy. In addition to presenting a fresh perspective on the correlation between synthesis methods and performance outcomes, this review offers a comprehensive overview of the limitations and challenges associated with LDH technologies. It provides valuable insights into the optimization process and practical considerations, making it an essential resource for advancing LDH technologies in real-world wastewater treatment applications.

制革厂和纺织业排放的污水中含有重金属、染料和抗金属细菌病原体，对水生生态系统造成了严重影响。本综述探讨了层状双氢氧化物（LDH）在应对这些环境挑战方面的潜力。文章全面分析了 LDH 的形态、合成技术以及在废水修复方面的性能。LDHs 是一种离子片状氢氧化物，主层中含有两种不同的金属阳离子，夹层中含有阴离子，由于其易于合成和独特的性质，已经引起了大量的研究兴趣。本综述与众不同之处在于将 LDHs 的各种合成方法与其在废水修复中的功效直接联系起来，提供了其他综述通常未涉及的见解。此外，本综述还探讨了层间阴离子（如碳酸盐和硫酸盐）在决定 LDHs 的结构、化学和物理性质方面的关键作用。综述还探讨了氮化石墨碳（gC3N4）和石墨烯基材料的改性如何通过增加表面积、延迟电荷重组以及改善吸附和光催化活性来提高 LDH 的性能。综述评估了这些因素对去除废水中污染物的影响，并深入讨论了污染物去除所涉及的机制，包括吸附、离子交换和光催化。报告还强调了 LDHs 的抗菌特性，尤其是在与先进材料相结合时，展示了其潜在的抗菌功效。除了以全新的视角探讨合成方法与性能结果之间的关系外，本综述还全面概述了与 LDH 技术相关的局限性和挑战。它为优化过程和实际考虑因素提供了宝贵的见解，使其成为在实际废水处理应用中推进 LDH 技术的重要资源。

{"title":"Layered double hydroxides for industrial wastewater remediation: A review","authors":"Sudarshan Sarkar, Chandan Upadhyay","doi":"10.1016/j.cattod.2024.115101","DOIUrl":"10.1016/j.cattod.2024.115101","url":null,"abstract":"<div><div>Tanneries and textile industries significantly impact aquatic ecosystems through the discharge of effluents containing heavy metals, dyes, and metal-resistant bacterial pathogens. This review examines the potential of layered double hydroxides (LDHs) for addressing these environmental challenges. It offers a comprehensive analysis of LDH morphology, synthesis techniques, and performance in wastewater remediation. LDHs are ionic lamellar hydroxides, containing two different metal cations in the main layers and anionic species in the interlayer, have attracted substantial research interest due to their ease of synthesis and unique properties. This review distinguishes itself by correlating various synthesis methods for LDHs directly with their efficacy in wastewater remediation, offering insights not typically covered in other reviews. Furthermore, the review explores the critical role of interlayer anions, such as carbonate and sulfate, in determining its influence in the structural, chemical, and physical properties of LDHs. It also addresses how modifications with graphitic carbon nitride (gC3N4) and graphene-based materials enhance LDH’s performance by increasing surface area, delaying charge recombination, and improving adsorption and photocatalytic activity. he review evaluates the impact of these factors on the removal of pollutants from wastewater and provides an in-depth discussion of the mechanisms involved in pollutant removal, including adsorption, ion exchange, and photocatalysis. It also highlights the antibacterial properties of LDHs, particularly when combined with advanced materials, demonstrating their potential antimicrobial efficacy. In addition to presenting a fresh perspective on the correlation between synthesis methods and performance outcomes, this review offers a comprehensive overview of the limitations and challenges associated with LDH technologies. It provides valuable insights into the optimization process and practical considerations, making it an essential resource for advancing LDH technologies in real-world wastewater treatment applications.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115101"},"PeriodicalIF":5.2,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ethyl esters synthesis catalyzed by lipase B from Candida antarctica immobilized on NiFe2O4 magnetic nanoparticles 固定在 NiFe2O4 磁性纳米粒子上的白色念珠菌脂肪酶 B 催化的乙酯合成

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2024-10-18 DOI: 10.1016/j.cattod.2024.115099

Gabrielle A.R. da Silva , Thamires M. de L.O. da Silva , João Paulo da S.Q. Menezes , Elizabeth Cristina T. Veloso , Gizele C. Fontes-Sant’Ana , Noemi Raquel C. Huaman , Rodrigo Brackmann , Marta A.P. Langone

The development of heterogeneous biocatalysts allows the expansion of the application of enzymes in different industrial processes, favoring the establishment of clean technologies. This work investigates the capacity of nickel ferrite magnetic nanoparticles (NiFe₂O₄) as a support for lipase B from Candida antarctica (CalB) immobilization. The adsorption capacity of the support revealed a maximum value of 15 mg_protein/g_support, according to the Langmuir isotherm model. Efficiency immobilization by physical adsorption was low (21.3 %), and CalB was covalently immobilized after functionalization of NiFe₂O₄ with APTMS (3-aminopropyl trimethoxysilane) and activation with glutaraldehyde (GA), showing higher immobilization yield (62.9 %). The spinel ferrite NiFe₂O₄ was characterized by many physicochemical analyses. The enzyme derivatives obtained (NiFe₂O₄-CalB and NiFe₂O₄-APTMS-GA-CalB) were evaluated in the synthesis of alkyl esters. Despite no production was observed in the transesterification reactions, esterification led to 37.3 ± 1.0 % and 62.1 ± 0.2 % of oleic acid conversions using NiFe₂O₄-APTMS-GA-CalB and NiFe₂O₄-CalB, respectively. After 4 cycles, NiFe₂O₄-CalB maintained 92 % of its initial activity. Nickel ferrite magnetic nanoparticles form an efficient heterogeneous catalyst with lipase, which could be used to remove the content of free fatty acids (FFAs), like oleic acid, present in cheap raw materials to produce biodiesel.

异质生物催化剂的开发扩大了酶在不同工业流程中的应用，有利于建立清洁技术。这项工作研究了镍铁氧体磁性纳米颗粒（NiFe2O4）作为一种支持物对来自南极念珠菌（CalB）的脂肪酶 B 的固定能力。根据 Langmuir 等温线模型，吸附剂的最大吸附容量为 15 mg 蛋白/gsupport。物理吸附的固定化效率较低（21.3%），而用 APTMS（3-氨基丙基三甲氧基硅烷）对 NiFe2O4 进行功能化并用戊二醛（GA）活化后，CalB 被共价固定化，固定化率较高（62.9%）。对尖晶石铁氧体 NiFe2O4 进行了多种物理化学分析。获得的酶衍生物（NiFe2O4-CalB 和 NiFe2O4-APTMS-GA-CalB）在合成烷基酯时进行了评估。尽管在酯交换反应中没有观察到生成，但使用 NiFe2O4-APTMS-GA-CalB 和 NiFe2O4-CalB 进行酯交换时，油酸的转化率分别为 37.3 ± 1.0 % 和 62.1 ± 0.2 %。经过 4 个循环后，NiFe2O4-CalB 保持了其初始活性的 92%。镍铁氧体磁性纳米粒子与脂肪酶形成了一种高效的异相催化剂，可用于去除廉价原料中的游离脂肪酸（FFA）含量，如油酸，以生产生物柴油。

{"title":"Ethyl esters synthesis catalyzed by lipase B from Candida antarctica immobilized on NiFe2O4 magnetic nanoparticles","authors":"Gabrielle A.R. da Silva , Thamires M. de L.O. da Silva , João Paulo da S.Q. Menezes , Elizabeth Cristina T. Veloso , Gizele C. Fontes-Sant’Ana , Noemi Raquel C. Huaman , Rodrigo Brackmann , Marta A.P. Langone","doi":"10.1016/j.cattod.2024.115099","DOIUrl":"10.1016/j.cattod.2024.115099","url":null,"abstract":"<div><div>The development of heterogeneous biocatalysts allows the expansion of the application of enzymes in different industrial processes, favoring the establishment of clean technologies. This work investigates the capacity of nickel ferrite magnetic nanoparticles (NiFe2O4) as a support for lipase B from Candida antarctica (CalB) immobilization. The adsorption capacity of the support revealed a maximum value of 15 mgprotein/gsupport, according to the Langmuir isotherm model. Efficiency immobilization by physical adsorption was low (21.3 %), and CalB was covalently immobilized after functionalization of NiFe2O4 with APTMS (3-aminopropyl trimethoxysilane) and activation with glutaraldehyde (GA), showing higher immobilization yield (62.9 %). The spinel ferrite NiFe2O4 was characterized by many physicochemical analyses. The enzyme derivatives obtained (NiFe2O4-CalB and NiFe2O4-APTMS-GA-CalB) were evaluated in the synthesis of alkyl esters. Despite no production was observed in the transesterification reactions, esterification led to 37.3 ± 1.0 % and 62.1 ± 0.2 % of oleic acid conversions using NiFe2O4-APTMS-GA-CalB and NiFe2O4-CalB, respectively. After 4 cycles, NiFe2O4-CalB maintained 92 % of its initial activity. Nickel ferrite magnetic nanoparticles form an efficient heterogeneous catalyst with lipase, which could be used to remove the content of free fatty acids (FFAs), like oleic acid, present in cheap raw materials to produce biodiesel.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"445 ","pages":"Article 115099"},"PeriodicalIF":5.2,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0