This study examines the catalytic activity of NiFeCoOx catalysts for anion exchange membrane (AEM) water electrolysis. The catalysts were synthesized with a Ni to Co ratio of 2:1 and Fe content ranges from 2.5 to 12.5 wt%. The catalysts were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The catalytic activity of the NiFeCoOx catalysts was evaluated through linear sweep voltammetry (LSV) and chronoamperometry (CA) experiments for the oxygen evolution reaction (OER). The catalyst with 5% Fe content exhibited the highest catalytic activity, achieving an overpotential of 228 mV at a current density of 10 mA cm−2. Long-term catalyst testing for the OER at 50 mA cm−2 showed stable electrolysis operation for 100 h. The catalyst was further analyzed in an AEM water electrolyzer in a single-cell test, and the NiFeCoOx catalyst with 5% Fe at the anode demonstrated the highest current densities of 1516 mA cm−2 and 1620 mA cm−2 at 55 °C and 70 °C at 2.1 V. The maximum current density of 1880 mA cm−2 was achieved at 2.2 V and 70 °C. The Nyquist plot analysis of electrolysis at 55 °C showed that the NiFeCoOx catalyst with 5% Fe had lower activation resistance compared with the other Fe loadings, indicating enhanced performance. The durability test was performed for 8 h, showing stable AEM water electrolysis with minimum degradation. An overall cell efficiency of 70.5% was achieved for the operation carried out at a higher current density of 0.8 A cm−2.
本研究探讨了用于阴离子交换膜（AEM）水电解的 NiFeCoOx 催化剂的催化活性。催化剂的镍钴比为 2:1，铁含量为 2.5 至 12.5 wt%。使用扫描电子显微镜（SEM）和 X 射线衍射（XRD）技术对催化剂进行了表征。通过线性扫频伏安法（LSV）和氧进化反应（OER）的计时安培计（CA）实验评估了 NiFeCoOx 催化剂的催化活性。铁含量为 5%的催化剂表现出最高的催化活性，在电流密度为 10 mA cm-2 时，过电位为 228 mV。催化剂在 AEM 水电解槽中进行了进一步的单电池测试分析，阳极含 5%铁的 NiFeCoOx 催化剂在 2.1 V、55 ℃ 和 70 ℃ 的条件下分别表现出 1516 mA cm-2 和 1620 mA cm-2 的最高电流密度。在 2.2 V 和 70 °C 时，最大电流密度为 1880 mA cm-2。55 °C电解的奈奎斯特图分析表明，与其他铁负载相比，含 5%铁的镍铁钴氧体催化剂的活化电阻较低，表明其性能有所提高。进行了 8 小时的耐久性测试，结果表明 AEM 水电解效果稳定，降解程度最低。在 0.8 A cm-2 的较高电流密度下运行时，电池总效率达到 70.5%。
{"title":"Performance Evaluation and Durability Analysis of NiFeCoOx Catalysts for Alkaline Water Electrolysis in Anion Exchange Membrane Electrolyzers","authors":"K. W. Ahmed, Michael Fowler","doi":"10.3390/catal14050322","DOIUrl":"https://doi.org/10.3390/catal14050322","url":null,"abstract":"This study examines the catalytic activity of NiFeCoOx catalysts for anion exchange membrane (AEM) water electrolysis. The catalysts were synthesized with a Ni to Co ratio of 2:1 and Fe content ranges from 2.5 to 12.5 wt%. The catalysts were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The catalytic activity of the NiFeCoOx catalysts was evaluated through linear sweep voltammetry (LSV) and chronoamperometry (CA) experiments for the oxygen evolution reaction (OER). The catalyst with 5% Fe content exhibited the highest catalytic activity, achieving an overpotential of 228 mV at a current density of 10 mA cm−2. Long-term catalyst testing for the OER at 50 mA cm−2 showed stable electrolysis operation for 100 h. The catalyst was further analyzed in an AEM water electrolyzer in a single-cell test, and the NiFeCoOx catalyst with 5% Fe at the anode demonstrated the highest current densities of 1516 mA cm−2 and 1620 mA cm−2 at 55 °C and 70 °C at 2.1 V. The maximum current density of 1880 mA cm−2 was achieved at 2.2 V and 70 °C. The Nyquist plot analysis of electrolysis at 55 °C showed that the NiFeCoOx catalyst with 5% Fe had lower activation resistance compared with the other Fe loadings, indicating enhanced performance. The durability test was performed for 8 h, showing stable AEM water electrolysis with minimum degradation. An overall cell efficiency of 70.5% was achieved for the operation carried out at a higher current density of 0.8 A cm−2.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":"93 19","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140978574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qian Tang, Shanshan Li, Liping Zhou, Lili Sun, Juan Xin, Wei Li
A self-sufficient bifunctional enzyme integrating reductive amination and coenzyme regeneration activities was developed and successfully employed to synthesize (S)-cyclopropylglycine with an improved reaction rate 2.1-fold over the native enzymes and a short bioconversion period of 6 h at a high substrate concentration of 120 g·L−1 and space–time yield of (S)-cyclopropylglycine up to 377.3 g·L−1·d−1, higher than that of any previously reported data. Additionally, (S)-cyclopropylglycine could be continuously synthesized for 90 h with the enzymes packed in a dialysis tube, providing 634.6 g of (S)-cyclopropylglycine with >99.5% ee and over 95% conversion yield up to 12 changes. These results confirmed that the newly developed NADH-driven biocatalytic system could be utilized as a self-sufficient biocatalyst for industrial application in the synthesis of (S)-cyclopropylglycine, which provides a chiral center and cyclopropyl fragment for the frequent synthesis of preclinical/clinical drug molecules.
{"title":"Facile Asymmetric Syntheses of Non-Natural Amino Acid (S)-Cyclopropylglycine by the Developed NADH-Driven Biocatalytic System","authors":"Qian Tang, Shanshan Li, Liping Zhou, Lili Sun, Juan Xin, Wei Li","doi":"10.3390/catal14050321","DOIUrl":"https://doi.org/10.3390/catal14050321","url":null,"abstract":"A self-sufficient bifunctional enzyme integrating reductive amination and coenzyme regeneration activities was developed and successfully employed to synthesize (S)-cyclopropylglycine with an improved reaction rate 2.1-fold over the native enzymes and a short bioconversion period of 6 h at a high substrate concentration of 120 g·L−1 and space–time yield of (S)-cyclopropylglycine up to 377.3 g·L−1·d−1, higher than that of any previously reported data. Additionally, (S)-cyclopropylglycine could be continuously synthesized for 90 h with the enzymes packed in a dialysis tube, providing 634.6 g of (S)-cyclopropylglycine with >99.5% ee and over 95% conversion yield up to 12 changes. These results confirmed that the newly developed NADH-driven biocatalytic system could be utilized as a self-sufficient biocatalyst for industrial application in the synthesis of (S)-cyclopropylglycine, which provides a chiral center and cyclopropyl fragment for the frequent synthesis of preclinical/clinical drug molecules.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":"12 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140984125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Having a comprehensive knowledge of phase equilibrium is advantageous for industrial simulation and design of chemical processes. For further acquisition of primary data to facilitate the separation and purification of waste oil biodiesel systems, a liquid–liquid equilibrium (LLE) tank is deployed for the ternary system of waste oil biodiesel + methanol + glycerin, thereby enhancing the precision and efficiency of the process. The phase equilibrium system was constructed under the influence of atmospheric pressure at precise temperatures of 303.15 K, 313.15 K, and 323.15 K. The equilibrium components of each substance were analyzed by employing high-temperature gas chromatography, a sophisticated analytical method that enables the identification and quantification of individual components of a sample. Moreover, the ternary liquid–liquid equilibrium data were correlated by implementing the NRTL and UNIQUAC activity coefficient models. Subsequently, the binary interaction parameters of the ternary system were derived by conducting regression analysis. The experimental data demonstrated that the presence of lower methanol content in the system resulted in nearly immiscible biodiesel and glycerol phases, which ultimately facilitated the separation of biodiesel and glycerol. Conversely, with the increase in methanol content, the mutual solubility of biodiesel and glycerol was observed to increase gradually. The results showed that the calculated values of the NRTL and UNIQUAC models aligned well with the experimental values. The root-mean-square deviations of the NRTL and UNIQUAC models at 313.15 K were 2.76% and 3.56%, respectively.
掌握全面的相平衡知识对于化学过程的工业模拟和设计非常有利。为了进一步获取原始数据，促进废油生物柴油系统的分离和提纯，我们为废油生物柴油+甲醇+甘油三元系统配置了一个液-液平衡（LLE）罐，从而提高了工艺的精度和效率。在 303.15 K、313.15 K 和 323.15 K 的精确温度下，在大气压力的影响下构建了相平衡系统。采用高温气相色谱法对每种物质的平衡组分进行了分析，这是一种复杂的分析方法，能够识别和量化样品中的单个组分。此外，还采用 NRTL 和 UNIQUAC 活性系数模型对三元液-液平衡数据进行了关联分析。随后，通过回归分析得出了三元体系的二元相互作用参数。实验数据表明，体系中甲醇含量较低时，生物柴油相和甘油相几乎不相溶，这最终促进了生物柴油和甘油的分离。相反，随着甲醇含量的增加，生物柴油和甘油的互溶性逐渐增加。结果表明，NRTL 和 UNIQUAC 模型的计算值与实验值十分吻合。在 313.15 K 时，NRTL 和 UNIQUAC 模型的均方根偏差分别为 2.76% 和 3.56%。
{"title":"Liquid–Liquid Equilibrium Behavior of Ternary Systems Comprising Biodiesel + Glycerol and Triglyceride + Methanol: Experimental Data and Modeling","authors":"Lingmei Yang, Shiyou Xing, Xianbin Teng, Rukuan Liu, Zhongming Wang, Baining Lin, Pengmei Lv, Akram Ali Nasser Mansoor Al-Haimi, Fatma Yehia, Wen Luo","doi":"10.3390/catal14050320","DOIUrl":"https://doi.org/10.3390/catal14050320","url":null,"abstract":"Having a comprehensive knowledge of phase equilibrium is advantageous for industrial simulation and design of chemical processes. For further acquisition of primary data to facilitate the separation and purification of waste oil biodiesel systems, a liquid–liquid equilibrium (LLE) tank is deployed for the ternary system of waste oil biodiesel + methanol + glycerin, thereby enhancing the precision and efficiency of the process. The phase equilibrium system was constructed under the influence of atmospheric pressure at precise temperatures of 303.15 K, 313.15 K, and 323.15 K. The equilibrium components of each substance were analyzed by employing high-temperature gas chromatography, a sophisticated analytical method that enables the identification and quantification of individual components of a sample. Moreover, the ternary liquid–liquid equilibrium data were correlated by implementing the NRTL and UNIQUAC activity coefficient models. Subsequently, the binary interaction parameters of the ternary system were derived by conducting regression analysis. The experimental data demonstrated that the presence of lower methanol content in the system resulted in nearly immiscible biodiesel and glycerol phases, which ultimately facilitated the separation of biodiesel and glycerol. Conversely, with the increase in methanol content, the mutual solubility of biodiesel and glycerol was observed to increase gradually. The results showed that the calculated values of the NRTL and UNIQUAC models aligned well with the experimental values. The root-mean-square deviations of the NRTL and UNIQUAC models at 313.15 K were 2.76% and 3.56%, respectively.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":"109 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140986767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bimetallic AuCu/SiO2 nanosized catalysts were prepared using the wet chemical reduction technique. From among Au0.1–1.5Cu10/SiO2 catalysts, the Au0.5Cu10/SiO2 catalyst gave the highest yield of calcium lactate of 87% at a glycerol conversion of 96% when the reaction of glycerol with calcium hydroxide at a mole ratio of calcium hydroxide to glycerol of 0.8:1 was conducted under an anaerobic atmosphere at 200 °C for 2 h. The interactions between metallic Au0 and Cu0 nanoparticles facilitate calcium lactate formation. The simulation of glycerol consumption rate with an empirical power-function reaction kinetics equation yielded a reaction activation energy of 44.3 kJ∙mol−1, revealing that the catalytic reaction of glycerol with calcium hydroxide to calcium lactate can be conducted by overcoming a mild energy barrier. The synthesis of calcium lactate through the catalytic reaction of glycerol with calcium hydroxide on a bimetallic AuCu/SiO2 nanosized catalyst under a safe anaerobic atmosphere is an alternative to the conventional calcium lactate production technique through the reaction of expensive lactic acid with calcium hydroxide.
{"title":"Direct Synthesis of Calcium Lactate through the Reaction of Glycerol with Calcium Hydroxide Catalyzed by Bimetallic AuCu/SiO2 Nanocatalysts","authors":"Changqing Li, Xinyue Cui, Aili Wang, Hengbo Yin, Yuting Li, Qiao Lin, Junjie Guo","doi":"10.3390/catal14050318","DOIUrl":"https://doi.org/10.3390/catal14050318","url":null,"abstract":"Bimetallic AuCu/SiO2 nanosized catalysts were prepared using the wet chemical reduction technique. From among Au0.1–1.5Cu10/SiO2 catalysts, the Au0.5Cu10/SiO2 catalyst gave the highest yield of calcium lactate of 87% at a glycerol conversion of 96% when the reaction of glycerol with calcium hydroxide at a mole ratio of calcium hydroxide to glycerol of 0.8:1 was conducted under an anaerobic atmosphere at 200 °C for 2 h. The interactions between metallic Au0 and Cu0 nanoparticles facilitate calcium lactate formation. The simulation of glycerol consumption rate with an empirical power-function reaction kinetics equation yielded a reaction activation energy of 44.3 kJ∙mol−1, revealing that the catalytic reaction of glycerol with calcium hydroxide to calcium lactate can be conducted by overcoming a mild energy barrier. The synthesis of calcium lactate through the catalytic reaction of glycerol with calcium hydroxide on a bimetallic AuCu/SiO2 nanosized catalyst under a safe anaerobic atmosphere is an alternative to the conventional calcium lactate production technique through the reaction of expensive lactic acid with calcium hydroxide.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" January","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140989851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Roshni Sajiv Kumar, J. Mmbaga, N. Semagina, Robert E. Hayes
Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes.
{"title":"Methane Combustion Kinetics over Palladium-Based Catalysts: Review and Modelling Guidelines","authors":"Roshni Sajiv Kumar, J. Mmbaga, N. Semagina, Robert E. Hayes","doi":"10.3390/catal14050319","DOIUrl":"https://doi.org/10.3390/catal14050319","url":null,"abstract":"Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 434","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140989983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xun Sun, Wenrui Lv, Yanan Cheng, H. Su, Libo Sun, Lijun Zhao, Zifan Wang, C. Qi
Semi-hydrogenation of acetylene to ethylene over metal oxide-supported Au nanoparticles is an interesting topic. Here, a hydrotalcite-based MMgAlOx (M=Cu, Ni, and Co) composite oxide was exploited by introducing different Cu, Ni, and Co dopants with unique properties, and then used as support to obtain Au/MMgAlOx catalysts via a modified deposition–precipitation method. XRD, BET, ICP-OES, TEM, Raman, XPS, and TPD were employed to investigate their physic-chemical properties and catalytic performances for the semi-hydrogenation of acetylene to ethylene. Generally, the catalytic activity of the Cu-modified Au/CuMgAlOx catalyst was higher than that of the other modified catalysts. The TOR for Au/CuMgAlOx was 0.0598 h−1, which was 30 times higher than that of Au/MgAl2O4. The SEM and XRD results showed no significant difference in structure or morphology after introducing the dopants. These dopants had an unfavorable effect on the Au particle size, as confirmed by the TEM studies. Accordingly, the effects on catalytic performance of the M dopant of the obtained Au/MMgAlOx catalyst were improved. Results of Raman, NH3-TPD, and CO2-TPD confirmed that the Au/CuMgAlOx catalyst had more basic sites, which is beneficial for less coking on the catalyst surface after the reaction. XPS analysis showed that gold nanoparticles exhibited a partially oxidized state at the edges and surfaces of CuMgAlOx. Besides an increased proportion of basic sites on Au/CuMgAlOx catalysts, the charge transfer from nanogold to the Cu-doped matrix support probably played a positive role in the selective hydrogenation of acetylene. The stability and deactivation of Au/CuMgAlOx catalysts were also discussed and a possible reaction mechanism was proposed.
{"title":"Au Nanoparticles Supported on Hydrotalcite-Based MMgAlOx (M=Cu, Ni, and Co) Composite: Influence of Dopants on the Catalytic Activity for Semi-Hydrogenation of C2H2","authors":"Xun Sun, Wenrui Lv, Yanan Cheng, H. Su, Libo Sun, Lijun Zhao, Zifan Wang, C. Qi","doi":"10.3390/catal14050315","DOIUrl":"https://doi.org/10.3390/catal14050315","url":null,"abstract":"Semi-hydrogenation of acetylene to ethylene over metal oxide-supported Au nanoparticles is an interesting topic. Here, a hydrotalcite-based MMgAlOx (M=Cu, Ni, and Co) composite oxide was exploited by introducing different Cu, Ni, and Co dopants with unique properties, and then used as support to obtain Au/MMgAlOx catalysts via a modified deposition–precipitation method. XRD, BET, ICP-OES, TEM, Raman, XPS, and TPD were employed to investigate their physic-chemical properties and catalytic performances for the semi-hydrogenation of acetylene to ethylene. Generally, the catalytic activity of the Cu-modified Au/CuMgAlOx catalyst was higher than that of the other modified catalysts. The TOR for Au/CuMgAlOx was 0.0598 h−1, which was 30 times higher than that of Au/MgAl2O4. The SEM and XRD results showed no significant difference in structure or morphology after introducing the dopants. These dopants had an unfavorable effect on the Au particle size, as confirmed by the TEM studies. Accordingly, the effects on catalytic performance of the M dopant of the obtained Au/MMgAlOx catalyst were improved. Results of Raman, NH3-TPD, and CO2-TPD confirmed that the Au/CuMgAlOx catalyst had more basic sites, which is beneficial for less coking on the catalyst surface after the reaction. XPS analysis showed that gold nanoparticles exhibited a partially oxidized state at the edges and surfaces of CuMgAlOx. Besides an increased proportion of basic sites on Au/CuMgAlOx catalysts, the charge transfer from nanogold to the Cu-doped matrix support probably played a positive role in the selective hydrogenation of acetylene. The stability and deactivation of Au/CuMgAlOx catalysts were also discussed and a possible reaction mechanism was proposed.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 24","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140991691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Taylor Mackenzie Fisher, Alexsando J. dos Santos, Sergi Garcia-Segura
This study explores the use of the iron-containing metal–organic framework (MOF), Basolite®F300, as a heterogeneous catalyst for electrochemically-driven Fenton processes. Electrochemical advanced oxidation processes (EAOPs) have shown promise on the abatement of recalcitrant organic pollutants such as pharmaceuticals. Tetracyclines (TC) are a frequently used class of antibiotics that are now polluting surface water and groundwater sources worldwide. Acknowledging the fast capability of EAOPs to treat persistent pharmaceutical pollutants, we propose an electrochemical Fenton treatment process that is catalyzed by the use of a commercially available MOF material to degrade TC. The efficiency of H2O2 generation in the IrO2/carbon felt setup is highlighted. However, electrochemical oxidation with H2O2 production (ECO-H2O2) alone is not enough to achieve complete TC removal, attributed to the formation of weak oxidant species. Incorporating Basolite®F300 in the heterogeneous electro-Fenton (HEF) process results in complete TC removal within 40 min, showcasing its efficacy. Additionally, this study explores the effect of varying MOF concentrations, indicating optimal removal rates at 100 mg L−1 due to a balance of kinetics and limitation of active sites of the catalysts. Furthermore, the impact of the applied current on TC removal is investigated, revealing a proportional relationship between current and removal rates. The analysis of energy efficiency emphasizes 50 mA as the optimal current, however, balancing removal efficiency with electrical energy consumption. This work highlights the potential of Basolite®F300 as an effective catalyst in the HEF process for pollutant abatement, providing valuable insights into optimizing electrified water treatment applications with MOF nanomaterials to treat organic pollutants.
{"title":"Metal–Organic Framework Fe-BTC as Heterogeneous Catalyst for Electro-Fenton Treatment of Tetracycline","authors":"Taylor Mackenzie Fisher, Alexsando J. dos Santos, Sergi Garcia-Segura","doi":"10.3390/catal14050314","DOIUrl":"https://doi.org/10.3390/catal14050314","url":null,"abstract":"This study explores the use of the iron-containing metal–organic framework (MOF), Basolite®F300, as a heterogeneous catalyst for electrochemically-driven Fenton processes. Electrochemical advanced oxidation processes (EAOPs) have shown promise on the abatement of recalcitrant organic pollutants such as pharmaceuticals. Tetracyclines (TC) are a frequently used class of antibiotics that are now polluting surface water and groundwater sources worldwide. Acknowledging the fast capability of EAOPs to treat persistent pharmaceutical pollutants, we propose an electrochemical Fenton treatment process that is catalyzed by the use of a commercially available MOF material to degrade TC. The efficiency of H2O2 generation in the IrO2/carbon felt setup is highlighted. However, electrochemical oxidation with H2O2 production (ECO-H2O2) alone is not enough to achieve complete TC removal, attributed to the formation of weak oxidant species. Incorporating Basolite®F300 in the heterogeneous electro-Fenton (HEF) process results in complete TC removal within 40 min, showcasing its efficacy. Additionally, this study explores the effect of varying MOF concentrations, indicating optimal removal rates at 100 mg L−1 due to a balance of kinetics and limitation of active sites of the catalysts. Furthermore, the impact of the applied current on TC removal is investigated, revealing a proportional relationship between current and removal rates. The analysis of energy efficiency emphasizes 50 mA as the optimal current, however, balancing removal efficiency with electrical energy consumption. This work highlights the potential of Basolite®F300 as an effective catalyst in the HEF process for pollutant abatement, providing valuable insights into optimizing electrified water treatment applications with MOF nanomaterials to treat organic pollutants.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 21","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140992239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually >USD 10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances, and pharmaceuticals, the need for them will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established and newer experimental methods. A wide range of methods, utilising microporous and mesoporous catalysts, has been explored, including their preparation and modification before use in industry. Their potential drawbacks and benefits have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in the field of fine chemical production using micro- and mesoporous heterogeneous catalysts.
{"title":"A Comprehensive Review of Fine Chemical Production Using Metal-Modified and Acidic Microporous and Mesoporous Catalytic Materials","authors":"Joseph Lantos, Narendra Kumar, Basudeb Saha","doi":"10.3390/catal14050317","DOIUrl":"https://doi.org/10.3390/catal14050317","url":null,"abstract":"Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually >USD 10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances, and pharmaceuticals, the need for them will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established and newer experimental methods. A wide range of methods, utilising microporous and mesoporous catalysts, has been explored, including their preparation and modification before use in industry. Their potential drawbacks and benefits have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in the field of fine chemical production using micro- and mesoporous heterogeneous catalysts.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 18","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140992298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abdulaziz Al-Anazi, Omer Bellahwel, Kavitha C., J. Abu‐Dahrieh, A. Ibrahim, S. Santhosh, A. Abasaeed, A. Fakeeha, Ahmed S. Al-Fatesh
Compared to steam reforming techniques, partial oxidation of methane (POM) is a promising technology to improve the efficiency of synthesizing syngas, which is a mixture of CO and H2. In this study, partial oxidation of methane (POM) was used to create syngas, a combination of CO and H2, using the SAPO-5-supported Ni catalysts. Using the wetness impregnation process, laboratory-synthesized Ni promoted with Sr, Ce, and Cu was used to modify the SAPO-5 support. The characterization results demonstrated that Ni is appropriate for the POM due to its crystalline structure, improved metal support contact, and increased thermal stability with Sr, Ce, and Cu promoters. During POM at 600 °C, the synthesized 5Ni+1Sr/SAPO-5 catalyst sustained stability for 240 min on stream. While keeping the reactants stoichiometric ratio of (CH4:O2 = 2:1), the addition of Sr promoter and active metal Ni to the SAPO-5 increased the CH4 conversion from 41.13% to 49.11% and improved the H2/CO ratio of 3.33. SAPO-5-supported 5Ni+1Sr catalysts have great potential for industrial catalysis owing to their unique combination of several oxides. This composition not only boosts the catalyst’s activity but also promotes favorable physiochemical properties, resulting in improved production of syngas. Syngas is a valuable intermediate in various industrial processes.
与蒸汽转化技术相比，甲烷部分氧化（POM）是一种很有前途的技术，可提高合成合成气（一氧化碳和二氧化碳的混合物）的效率。本研究利用 SAPO-5 支持的镍催化剂，采用甲烷部分氧化（POM）技术制造 CO 和 H2 混合的合成气。采用湿法浸渍工艺，用实验室合成的镍促进锶、铈和铜对 SAPO-5 载体进行改性。表征结果表明，由于镍的结晶结构、金属支撑接触的改善以及与 Sr、Ce 和 Cu 促进剂的热稳定性的提高，镍非常适合用于 POM。在 600 °C 下进行 POM 反应时，合成的 5Ni+1Sr/SAPO-5 催化剂在 240 分钟内保持稳定。在保持反应物化学计量比（CH4:O2 = 2:1）的情况下，向 SAPO-5 添加 Sr 促进剂和活性金属 Ni 可将 CH4 转化率从 41.13% 提高到 49.11%，并将 H2/CO 比率提高到 3.33。SAPO-5支撑的5Ni+1Sr催化剂具有多种氧化物的独特组合，因此在工业催化方面具有巨大潜力。这种组合不仅能提高催化剂的活性，还能促进其良好的理化特性，从而提高合成气的产量。合成气是各种工业流程中的重要中间产物。
{"title":"Promoter Impact on 5Ni/SAPO-5 Catalyst for H2 Production via Methane Partial Oxidation","authors":"Abdulaziz Al-Anazi, Omer Bellahwel, Kavitha C., J. Abu‐Dahrieh, A. Ibrahim, S. Santhosh, A. Abasaeed, A. Fakeeha, Ahmed S. Al-Fatesh","doi":"10.3390/catal14050316","DOIUrl":"https://doi.org/10.3390/catal14050316","url":null,"abstract":"Compared to steam reforming techniques, partial oxidation of methane (POM) is a promising technology to improve the efficiency of synthesizing syngas, which is a mixture of CO and H2. In this study, partial oxidation of methane (POM) was used to create syngas, a combination of CO and H2, using the SAPO-5-supported Ni catalysts. Using the wetness impregnation process, laboratory-synthesized Ni promoted with Sr, Ce, and Cu was used to modify the SAPO-5 support. The characterization results demonstrated that Ni is appropriate for the POM due to its crystalline structure, improved metal support contact, and increased thermal stability with Sr, Ce, and Cu promoters. During POM at 600 °C, the synthesized 5Ni+1Sr/SAPO-5 catalyst sustained stability for 240 min on stream. While keeping the reactants stoichiometric ratio of (CH4:O2 = 2:1), the addition of Sr promoter and active metal Ni to the SAPO-5 increased the CH4 conversion from 41.13% to 49.11% and improved the H2/CO ratio of 3.33. SAPO-5-supported 5Ni+1Sr catalysts have great potential for industrial catalysis owing to their unique combination of several oxides. This composition not only boosts the catalyst’s activity but also promotes favorable physiochemical properties, resulting in improved production of syngas. Syngas is a valuable intermediate in various industrial processes.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140994074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrea Osti, Lorenzo Rizzato, Jonathan Cavazzani, Ambra Meneghello, Antonella Glisenti
The imperative reduction of carbon dioxide into valuable fuels stands as a crucial step in the transition towards a more sustainable energy system. Perovskite oxides, with their high compositional and property adjustability, emerge as promising catalysts for this purpose, whether employed independently or as a supporting matrix for other active metals. In this study, an A-site-deficient La0.9FeO3 perovskite underwent surface decoration with Ni, Cu or Ni + Cu via a citric acid-templated wet impregnation method. Following extensive characterization through XRD, N2 physisorption, H2-TPR, SEM-EDX, HAADF STEM-EDX mapping, CO2-TPD and XPS, the prepared powders underwent reduction under diluted H2 to yield metallic nanoparticles (NPs). The prepared catalysts were then evaluated for CO2 reduction in a CO2/H2 = 1/4 mixture. The deposition of Ni or Cu NPs on the perovskite support significantly enhanced the conversion of CO2, achieving a 50% conversion rate at 500 °C, albeit resulting in only CO as the final product. Notably, the catalyst featuring Ni-Cu co-deposition outperformed in the intermediate temperature range, exhibiting high selectivity for CH4 production around 350 °C. For this latter catalyst, a synergistic effect of the metal–support interaction was evidenced by H2-TPR and CO2-TPD experiments as well as a better nanoparticle dispersion. A remarkable stability in a 20 h time-span was also demonstrated for all catalysts, especially the one with Ni-Cu co-deposition.
将二氧化碳还原成有价值的燃料是向更可持续的能源系统过渡的关键一步。透辉石氧化物具有很高的组成和性质可调节性，无论是单独使用还是作为其他活性金属的支撑基质，都是很有前途的催化剂。在本研究中，通过柠檬酸引发的湿浸渍法，用 Ni、Cu 或 Ni + Cu 对 A 盐缺失的 La0.9FeO3 包晶进行了表面装饰。在通过 XRD、N2 物理吸附、H2-TPR、SEM-EDX、HAADF STEM-EDX 制图、CO2-TPD 和 XPS 进行广泛表征后，制备的粉末在稀 H2 下进行还原，生成金属纳米颗粒 (NP)。然后对制备的催化剂在 CO2/H2 = 1/4 混合物中进行二氧化碳还原评估。在过氧化物载体上沉积 Ni 或 Cu NPs 能显著提高 CO2 的转化率，在 500 °C 时转化率达到 50%，尽管最终产物只有 CO。值得注意的是，以 Ni-Cu 共沉积为特征的催化剂在中间温度范围内表现更佳，在 350 °C 左右的 CH4 生产中表现出较高的选择性。对于后一种催化剂，H2-TPR 和 CO2-TPD 实验证明了金属-支撑相互作用的协同效应以及更好的纳米颗粒分散性。所有催化剂，尤其是镍铜共沉积催化剂，在 20 小时的时间跨度内都表现出了卓越的稳定性。
{"title":"Perovskite Oxide Catalysts for Enhanced CO2 Reduction: Embroidering Surface Decoration with Ni and Cu Nanoparticles","authors":"Andrea Osti, Lorenzo Rizzato, Jonathan Cavazzani, Ambra Meneghello, Antonella Glisenti","doi":"10.3390/catal14050313","DOIUrl":"https://doi.org/10.3390/catal14050313","url":null,"abstract":"The imperative reduction of carbon dioxide into valuable fuels stands as a crucial step in the transition towards a more sustainable energy system. Perovskite oxides, with their high compositional and property adjustability, emerge as promising catalysts for this purpose, whether employed independently or as a supporting matrix for other active metals. In this study, an A-site-deficient La0.9FeO3 perovskite underwent surface decoration with Ni, Cu or Ni + Cu via a citric acid-templated wet impregnation method. Following extensive characterization through XRD, N2 physisorption, H2-TPR, SEM-EDX, HAADF STEM-EDX mapping, CO2-TPD and XPS, the prepared powders underwent reduction under diluted H2 to yield metallic nanoparticles (NPs). The prepared catalysts were then evaluated for CO2 reduction in a CO2/H2 = 1/4 mixture. The deposition of Ni or Cu NPs on the perovskite support significantly enhanced the conversion of CO2, achieving a 50% conversion rate at 500 °C, albeit resulting in only CO as the final product. Notably, the catalyst featuring Ni-Cu co-deposition outperformed in the intermediate temperature range, exhibiting high selectivity for CH4 production around 350 °C. For this latter catalyst, a synergistic effect of the metal–support interaction was evidenced by H2-TPR and CO2-TPD experiments as well as a better nanoparticle dispersion. A remarkable stability in a 20 h time-span was also demonstrated for all catalysts, especially the one with Ni-Cu co-deposition.","PeriodicalId":505577,"journal":{"name":"Catalysts","volume":" 20","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140991392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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