Dehydration of i-PrOH is used in academic research as a test reaction to probe the acid properties of solid acid catalysts. Also, it has practical importance for the utilization of surplus acetone produced by the Hock process for the combined manufacturing of phenol and acetone as well as for the production of propene from renewable resources and waste. This study demonstrates the excellent performance of polyoxometalate acid catalysts comprising silica-supported Keggin-type heteropoly acids H3PW12O40 and H4SiW12O40 for gas-phase i-PrOH-to-propene dehydration at ambient pressure. These catalysts show similar efficacies, giving an i-PrOH conversion and propene selectivity of 96.8 and 99.7% for 25%HPW/SiO2 and 97.1 and 99.4% for 25%HSiW/SiO2 in a fixed-bed reactor at 120 °C, a relevant-to-practice i-PrOH partial pressure of 15 kPa and a contact time W/F = 27 g h mol−1 (GHSV = 900 mL g−1 h−1). The catalysts are stable, resisting deactivation for at least 24 h time on stream. The HPA/SiO2 catalysts are superior to aluminosilicate zeolites such as H-mordenite, HZSM-5 and HY for i-PrOH-to-propene dehydration in terms of i-PrOH conversion, propene selectivity and catalyst stability.
{"title":"Dehydration of Isopropanol over Silica-Supported Heteropoly Acids","authors":"Amal Alasmari, E. Kozhevnikova, I. Kozhevnikov","doi":"10.3390/catal14010051","DOIUrl":"https://doi.org/10.3390/catal14010051","url":null,"abstract":"Dehydration of i-PrOH is used in academic research as a test reaction to probe the acid properties of solid acid catalysts. Also, it has practical importance for the utilization of surplus acetone produced by the Hock process for the combined manufacturing of phenol and acetone as well as for the production of propene from renewable resources and waste. This study demonstrates the excellent performance of polyoxometalate acid catalysts comprising silica-supported Keggin-type heteropoly acids H3PW12O40 and H4SiW12O40 for gas-phase i-PrOH-to-propene dehydration at ambient pressure. These catalysts show similar efficacies, giving an i-PrOH conversion and propene selectivity of 96.8 and 99.7% for 25%HPW/SiO2 and 97.1 and 99.4% for 25%HSiW/SiO2 in a fixed-bed reactor at 120 °C, a relevant-to-practice i-PrOH partial pressure of 15 kPa and a contact time W/F = 27 g h mol−1 (GHSV = 900 mL g−1 h−1). The catalysts are stable, resisting deactivation for at least 24 h time on stream. The HPA/SiO2 catalysts are superior to aluminosilicate zeolites such as H-mordenite, HZSM-5 and HY for i-PrOH-to-propene dehydration in terms of i-PrOH conversion, propene selectivity and catalyst stability.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"7 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139438303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ismaila Mudi, Abarasi Hart, Andrew Ingram, Joseph Wood
Lignocellulosic biomass can uptake CO2 during growth, which can then be pyrolysed into three major products, biochar (BC), syngas, and bio-oil. Due to the presence of oxygenated organic compounds, the produced bio-oil is not suitable for direct use as a fuel and requires upgrading via hydrodeoxygenation (HDO) and hydrogenation. This is typically carried out over a supported metal catalyst. Regarding circular economy and sustainability, the BC from the pyrolysis step can potentially be activated and used as a novel catalyst support, as reported here. A 15 wt% Ni/BC catalyst was developed by chemically modifying BC with sulfuric acid to improve mesoporous structure and surface area. When compared to the pristine Ni/BC catalyst, sulfuric activated Ni/BC catalyst has excellent mesopores and a high surface area, which increases the dispersion of Ni nanoparticles and hence improves the adsorptive effect and thus catalytic performance. A liquid phase hydrogenation of furfural to 2-methylfuran was performed over the developed 15 wt% Ni/BC catalyst. Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic type models for adsorption of dissociative H2 were screened based on an R2 value greater than 99%, demonstrating that the experimental data satisfactorily fit to three plausible models: competitive (Model I), competitive at only one type of adsorption site (Model II), and non-competitive with two types of adsorption sites (Model III). With a correlation coefficient greater than 99% between the experimental rates and the predicted rate, Model III, which is a dual-site adsorption mechanism involving furfural adsorption and hydrogen dissociative adsorption and surface reaction, is the best fit. The Ni/BC catalyst demonstrated comparative performance and significant cost savings over previous catalysts; a value of 24.39 kJ mol−1 was estimated for activation energy, −11.43 kJ mol−1 for the enthalpy of adsorption for H2, and −5.86 kJ mol−1 for furfural. The developed Ni/BC catalyst demonstrated excellent stability in terms of conversion of furfural (96%) and yield of 2-methylfuran (54%) at the fourth successive experiments. Based on furfural conversion and yield of products, it appears that pores are constructed slowly during sulfuric acid activation of the biochar.
{"title":"A Kinetic Model of Furfural Hydrogenation to 2-Methylfuran on Nanoparticles of Nickel Supported on Sulfuric Acid-Modified Biochar Catalyst","authors":"Ismaila Mudi, Abarasi Hart, Andrew Ingram, Joseph Wood","doi":"10.3390/catal14010054","DOIUrl":"https://doi.org/10.3390/catal14010054","url":null,"abstract":"Lignocellulosic biomass can uptake CO2 during growth, which can then be pyrolysed into three major products, biochar (BC), syngas, and bio-oil. Due to the presence of oxygenated organic compounds, the produced bio-oil is not suitable for direct use as a fuel and requires upgrading via hydrodeoxygenation (HDO) and hydrogenation. This is typically carried out over a supported metal catalyst. Regarding circular economy and sustainability, the BC from the pyrolysis step can potentially be activated and used as a novel catalyst support, as reported here. A 15 wt% Ni/BC catalyst was developed by chemically modifying BC with sulfuric acid to improve mesoporous structure and surface area. When compared to the pristine Ni/BC catalyst, sulfuric activated Ni/BC catalyst has excellent mesopores and a high surface area, which increases the dispersion of Ni nanoparticles and hence improves the adsorptive effect and thus catalytic performance. A liquid phase hydrogenation of furfural to 2-methylfuran was performed over the developed 15 wt% Ni/BC catalyst. Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic type models for adsorption of dissociative H2 were screened based on an R2 value greater than 99%, demonstrating that the experimental data satisfactorily fit to three plausible models: competitive (Model I), competitive at only one type of adsorption site (Model II), and non-competitive with two types of adsorption sites (Model III). With a correlation coefficient greater than 99% between the experimental rates and the predicted rate, Model III, which is a dual-site adsorption mechanism involving furfural adsorption and hydrogen dissociative adsorption and surface reaction, is the best fit. The Ni/BC catalyst demonstrated comparative performance and significant cost savings over previous catalysts; a value of 24.39 kJ mol−1 was estimated for activation energy, −11.43 kJ mol−1 for the enthalpy of adsorption for H2, and −5.86 kJ mol−1 for furfural. The developed Ni/BC catalyst demonstrated excellent stability in terms of conversion of furfural (96%) and yield of 2-methylfuran (54%) at the fourth successive experiments. Based on furfural conversion and yield of products, it appears that pores are constructed slowly during sulfuric acid activation of the biochar.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"11 2","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139438750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luisa F. Navarrete, María Atienza-Martínez, I. Reyero, J. C. Urroz, Oihana Amorrortu, O. Sánz, Mario Montes, S. Garcés, F. Bimbela, Luis M. Gandía
Two series of Ni and Co catalysts supported onto La-Al2O3 were prepared and the CO2 hydrogenation reactions investigated. The catalytic performance was evaluated in terms of the evolution with the reaction temperature of the CO2 conversion and product (CH4 and CO) yields, as well as specific activities (TOF) and apparent activation energies. CH4 was the favored product over both metals while the TOF for CH4 formation was about three times higher for Ni than Co at 240–265 °C. Metallic particle size effects were found, with the TOF for CH4 formation decreasing over both Ni and Co as the mean metallic size decreased. In contrast, the TOF for CO formation tended to increase at a decreasing particle size for the catalysts with the smallest Ni particle sizes. The apparent activation energies for Ni and Co were very similar and significantly decreased to values of 73–79 kJ/mol when the metallic dispersion increased. The catalysts were prepared using the all-in-one method, resulting in (poly)vinyl alcohol (PVA) being a key additive that allowed us to enhance the dispersion of Ni and Co to give very effective catalysts. This comparative study joins the few existing ones in the literature in which catalysts based on these metals operated under strictly the same reaction conditions.
制备了两个系列的 Ni 和 Co 催化剂，并对其在 La-Al2O3 上的二氧化碳加氢反应进行了研究。根据 CO2 转化率和产物（CH4 和 CO）产率随反应温度的变化情况，以及比活度（TOF）和表观活化能，对催化性能进行了评估。在 240-265 °C 温度下，CH4 是两种金属都偏爱的产物，而 Ni 形成 CH4 的 TOF 比 Co 高约三倍。研究还发现了金属颗粒尺寸的影响，随着平均金属尺寸的减小，镍和钴形成 CH4 的 TOF 都会减小。相反，对于 Ni 粒子尺寸最小的催化剂，随着粒子尺寸的减小，CO 生成的 TOF 有增加的趋势。镍和钴的表观活化能非常相似，当金属分散度增加时，表观活化能明显降低至 73-79 kJ/mol 的值。催化剂的制备采用了多合一方法，其中（聚）乙烯醇（PVA）是一种关键添加剂，使我们能够提高镍和钴的分散度，从而制备出非常有效的催化剂。这项比较研究是对现有文献中基于这些金属的催化剂在严格相同的反应条件下运行的少数研究的补充。
{"title":"Comparative Study of Supported Ni and Co Catalysts Prepared Using the All-in-One Method in the Hydrogenation of CO2: Effects of Using (Poly)Vinyl Alcohol (PVA) as an Additive","authors":"Luisa F. Navarrete, María Atienza-Martínez, I. Reyero, J. C. Urroz, Oihana Amorrortu, O. Sánz, Mario Montes, S. Garcés, F. Bimbela, Luis M. Gandía","doi":"10.3390/catal14010047","DOIUrl":"https://doi.org/10.3390/catal14010047","url":null,"abstract":"Two series of Ni and Co catalysts supported onto La-Al2O3 were prepared and the CO2 hydrogenation reactions investigated. The catalytic performance was evaluated in terms of the evolution with the reaction temperature of the CO2 conversion and product (CH4 and CO) yields, as well as specific activities (TOF) and apparent activation energies. CH4 was the favored product over both metals while the TOF for CH4 formation was about three times higher for Ni than Co at 240–265 °C. Metallic particle size effects were found, with the TOF for CH4 formation decreasing over both Ni and Co as the mean metallic size decreased. In contrast, the TOF for CO formation tended to increase at a decreasing particle size for the catalysts with the smallest Ni particle sizes. The apparent activation energies for Ni and Co were very similar and significantly decreased to values of 73–79 kJ/mol when the metallic dispersion increased. The catalysts were prepared using the all-in-one method, resulting in (poly)vinyl alcohol (PVA) being a key additive that allowed us to enhance the dispersion of Ni and Co to give very effective catalysts. This comparative study joins the few existing ones in the literature in which catalysts based on these metals operated under strictly the same reaction conditions.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"10 11","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139439865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solar photocatalysis has evolved rapidly over the past few decades and has received significant attention for its green, safe and renewable energy benefits, particularly in the current era of global crisis, being considered as a potential solution to the major problems we face today, such as the shortage of fossil fuels and the impact of human activities on the environment [...]
{"title":"Editorial: Special Issue Entitled “Development of g-C3N4-Based Photocatalysts: Environmental Purification and Energy Conversion”","authors":"Feng Guo, Xue Lin, Yuanzhi Hong, Wei‐long Shi","doi":"10.3390/catal14010046","DOIUrl":"https://doi.org/10.3390/catal14010046","url":null,"abstract":"Solar photocatalysis has evolved rapidly over the past few decades and has received significant attention for its green, safe and renewable energy benefits, particularly in the current era of global crisis, being considered as a potential solution to the major problems we face today, such as the shortage of fossil fuels and the impact of human activities on the environment [...]","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"2 6","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139439933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The structure and performance stability of a Pt-based catalyst for propane dehydrogenation during its reaction–regeneration cycles is one of the key factors for its commercial application. A 0.3% Pt/Al2O3 catalyst with a sub-nanometric particle size was prepared and two different types of regeneration processes, long-term dichloroethane oxychlorination and a reaction–oxidation–oxychlorination cycle, were investigated on this catalyst. The fresh, sintered and regenerated catalyst was characterized by HAADF-STEM, CO-DRIFTS, XPS, CO chemisorption and N2 physisorption, and its catalytic performance for propane dehydrogenation was also tested. The results show that the catalysts tend to have a similar particle size, coordination environment and catalytic performance with the extension of the regeneration time or an increase in the number of cycles in the two regeneration processes, and a common steady state could be achieved on the catalysts. This indicates that structure of the catalyst tends to approach its equilibrium state in the regeneration process, during which the utilization efficiency of Pt is maximized by increasing the dispersion of Pt and its intrinsic activity, and the structural robustness is secured. The performance of the catalyst is comparable to that of a single-atom Pt/Al2O3 catalyst.
{"title":"Structure Robustness of Highly Dispersed Pt/Al2O3 Catalyst for Propane Dehydrogenation during Oxychlorination Regeneration Process","authors":"Lu Dong, Yitong Sun, Yifan Zhou, Zhijun Sui, Yunsheng Dai, Yian Zhu, Xinggui Zhou","doi":"10.3390/catal14010048","DOIUrl":"https://doi.org/10.3390/catal14010048","url":null,"abstract":"The structure and performance stability of a Pt-based catalyst for propane dehydrogenation during its reaction–regeneration cycles is one of the key factors for its commercial application. A 0.3% Pt/Al2O3 catalyst with a sub-nanometric particle size was prepared and two different types of regeneration processes, long-term dichloroethane oxychlorination and a reaction–oxidation–oxychlorination cycle, were investigated on this catalyst. The fresh, sintered and regenerated catalyst was characterized by HAADF-STEM, CO-DRIFTS, XPS, CO chemisorption and N2 physisorption, and its catalytic performance for propane dehydrogenation was also tested. The results show that the catalysts tend to have a similar particle size, coordination environment and catalytic performance with the extension of the regeneration time or an increase in the number of cycles in the two regeneration processes, and a common steady state could be achieved on the catalysts. This indicates that structure of the catalyst tends to approach its equilibrium state in the regeneration process, during which the utilization efficiency of Pt is maximized by increasing the dispersion of Pt and its intrinsic activity, and the structural robustness is secured. The performance of the catalyst is comparable to that of a single-atom Pt/Al2O3 catalyst.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"72 23","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139440607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nitrous oxide (N2O) is an industrial waste gas (e.g., from the production of adipic acid), which damages the ozone layer and causes the greenhouse effect. Density functional theory calculations were employed to investigate the mechanism of direct catalytic decomposition of N2O and selective catalytic reduction (SCR) of N2O by CO over Fe-ZSM-5 zeolites. Two stable Fe-active sites with six-membered ring structures on Fe-ZSM-5 were considered. The calculations indicate that the decomposition of N2O is affected by the coordination environment around Fe and can occur through two reaction pathways. However, there is invariably a more considerable energy hurdle for the initiation of the second stage of N2O decomposition. When CO participated in the reaction, it showed good reactivity and stability, the reaction energy barriers of the rate-limiting step were reduced by roughly 20.57 kcal/mol compared to the direct catalytic decomposition of N2O. CO exhibited a superior electron-donating ability and orbital hybridization performance during the reaction, which enhanced the cyclicity of the N2O reduction catalytic process. Our calculations confirmed the significant role of CO in N2O reduction over Fe-ZSM-5 observed in previous studies. This study provides a valuable theoretical reference for exploring CO-SCR methods for N2O reduction over Fe-based zeolite catalysts.
一氧化二氮（N2O）是一种工业废气（如己二酸生产过程中产生的废气），它会破坏臭氧层并导致温室效应。本研究采用密度泛函理论计算方法研究了 Fe-ZSM-5 沸石直接催化分解 N2O 和 CO 选择性催化还原 N2O 的机理。研究考虑了 Fe-ZSM-5 上具有六元环结构的两个稳定的 Fe 活性位点。计算结果表明，N2O 的分解受铁周围配位环境的影响，可通过两种反应途径进行。然而，在 N2O 分解的第二阶段，无一例外地存在着更大的能量障碍。当 CO 参与反应时，它表现出良好的反应活性和稳定性，与直接催化分解 N2O 相比，限速步骤的反应能垒大约降低了 20.57 kcal/mol。在反应过程中，CO 表现出卓越的电子供能能力和轨道杂化性能，这增强了 N2O 还原催化过程的循环性。我们的计算证实了以往研究中观察到的 CO 在 Fe-ZSM-5 上还原 N2O 过程中的重要作用。这项研究为探索在铁基沸石催化剂上还原 N2O 的 CO-SCR 方法提供了宝贵的理论参考。
{"title":"Density Functional Theory Study of Mechanism of Reduction of N2O by CO over Fe-ZSM-5 Zeolites","authors":"Ning Yuan, Congru Gao, Xiuliang Sun, Jianwei Li","doi":"10.3390/catal14010049","DOIUrl":"https://doi.org/10.3390/catal14010049","url":null,"abstract":"Nitrous oxide (N2O) is an industrial waste gas (e.g., from the production of adipic acid), which damages the ozone layer and causes the greenhouse effect. Density functional theory calculations were employed to investigate the mechanism of direct catalytic decomposition of N2O and selective catalytic reduction (SCR) of N2O by CO over Fe-ZSM-5 zeolites. Two stable Fe-active sites with six-membered ring structures on Fe-ZSM-5 were considered. The calculations indicate that the decomposition of N2O is affected by the coordination environment around Fe and can occur through two reaction pathways. However, there is invariably a more considerable energy hurdle for the initiation of the second stage of N2O decomposition. When CO participated in the reaction, it showed good reactivity and stability, the reaction energy barriers of the rate-limiting step were reduced by roughly 20.57 kcal/mol compared to the direct catalytic decomposition of N2O. CO exhibited a superior electron-donating ability and orbital hybridization performance during the reaction, which enhanced the cyclicity of the N2O reduction catalytic process. Our calculations confirmed the significant role of CO in N2O reduction over Fe-ZSM-5 observed in previous studies. This study provides a valuable theoretical reference for exploring CO-SCR methods for N2O reduction over Fe-based zeolite catalysts.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"49 7","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139441297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Flávio Pinheiro Valois, Kelly Christina Alves Bezerra, F. P. C. Assunção, Lucas Pinto Bernar, Simone Patrícia Aranha da Paz, Marcelo Costa Santos, Waldeci Paraguassu Feio, Renan Marcelo Pereira Silva, Neyson Mendonça, Douglas Alberto Rocha de Castro, Sergio Duvoisin Jr., Antônio Rafael Quadros Gomes, Victor Ricardo Costa Sousa, Marta Chagas Monteiro, N. Machado
Biomass-derived products are a promising way to substitute the necessity for petroleum-derived products, since lignocellulosic material is widely available in our atmosphere and contributes to the reduction of greenhouse gases (GHGs), due to zero net emissions of CO2. This study explores the impact of temperature and molarity on the pyrolysis of açaí seeds (Euterpe oleracea, Mart.) activated with KOH and subsequently on the yield of bio-oil, hydrocarbon content of bio-oil, antioxidant activity of bio-oil, and chemical composition of the aqueous phase. The experiments were carried out at 350, 400, and 450 °C and 1.0 atmosphere, with 2.0 M KOH, and at 450 °C and 1.0 atmosphere, with 0.5 M, 1.0 M, and 2.0 M KOH, at laboratory scale. The composition of bio-oils and the aqueous phase were determined by GC-MS, while the acid value, a physicochemical property of fundamental importance in biofuels, was determined by AOCS methods. The antioxidant activity of bio-oils was determined by the TEAC method. The solid phase (biochar) was characterized by X-ray diffraction (XRD). The diffractograms identified the presence of Kalicinite (KHCO3) in biochar, and those higher temperatures favor the formation peaks of Kalicinite (KHCO3). The pyrolysis of açaí seeds activated with KOH show bio-oil yields from 3.19 to 6.79 (wt.%), aqueous phase yields between 20.34 and 25.57 (wt.%), solid phase yields (coke) between 33.40 and 43.37 (wt.%), and gas yields from 31.85 to 34.45 (wt.%). The yield of bio-oil shows a smooth exponential increase with temperature. The acidity of bio-oil varied between 12.3 and 257.6 mg KOH/g, decreasing exponentially with temperature, while that of the aqueous phase varied between 17.9 and 118.9 mg KOH/g, showing an exponential decay behavior with temperature and demonstrating that higher temperatures favor not only the yield of bio-oil but also bio-oils with lower acidity. For the experiments with KOH activation, the GC-MS of bio-oil identified the presence of hydrocarbons (alkanes, alkenes, cycloalkanes, cycloalkenes, and aromatics) and oxygenates (carboxylic acids, phenols, ketones, and esters). The concentration of hydrocarbons varied between 10.19 and 25.71 (area.%), increasing with temperature, while that of oxygenates varied between 52.69 and 72.15 (area.%), decreasing with temperature. For the experiments with constant temperature, the concentrations of hydrocarbons in bio-oil increased exponentially with molarity, while those of oxygenates decreased exponentially, showing that higher molarities favor the formation of hydrocarbons in bio-oil. The antioxidant activity of bio-oils decreases with increasing temperature, as the content of phenolic compounds decreases, and it decreases with increasing KOH molarity, as higher molarities favor the formation of hydrocarbons. Finally, it can be concluded that chemical activation of açaí seeds with KOH favors not only the yield of bio-oil but also the content of hydrocarbons. The study of process
{"title":"Improving the Antioxidant Activity, Yield, and Hydrocarbon Content of Bio-Oil from the Pyrolysis of Açaí Seeds by Chemical Activation: Effect of Temperature and Molarity","authors":"Flávio Pinheiro Valois, Kelly Christina Alves Bezerra, F. P. C. Assunção, Lucas Pinto Bernar, Simone Patrícia Aranha da Paz, Marcelo Costa Santos, Waldeci Paraguassu Feio, Renan Marcelo Pereira Silva, Neyson Mendonça, Douglas Alberto Rocha de Castro, Sergio Duvoisin Jr., Antônio Rafael Quadros Gomes, Victor Ricardo Costa Sousa, Marta Chagas Monteiro, N. Machado","doi":"10.3390/catal14010044","DOIUrl":"https://doi.org/10.3390/catal14010044","url":null,"abstract":"Biomass-derived products are a promising way to substitute the necessity for petroleum-derived products, since lignocellulosic material is widely available in our atmosphere and contributes to the reduction of greenhouse gases (GHGs), due to zero net emissions of CO2. This study explores the impact of temperature and molarity on the pyrolysis of açaí seeds (Euterpe oleracea, Mart.) activated with KOH and subsequently on the yield of bio-oil, hydrocarbon content of bio-oil, antioxidant activity of bio-oil, and chemical composition of the aqueous phase. The experiments were carried out at 350, 400, and 450 °C and 1.0 atmosphere, with 2.0 M KOH, and at 450 °C and 1.0 atmosphere, with 0.5 M, 1.0 M, and 2.0 M KOH, at laboratory scale. The composition of bio-oils and the aqueous phase were determined by GC-MS, while the acid value, a physicochemical property of fundamental importance in biofuels, was determined by AOCS methods. The antioxidant activity of bio-oils was determined by the TEAC method. The solid phase (biochar) was characterized by X-ray diffraction (XRD). The diffractograms identified the presence of Kalicinite (KHCO3) in biochar, and those higher temperatures favor the formation peaks of Kalicinite (KHCO3). The pyrolysis of açaí seeds activated with KOH show bio-oil yields from 3.19 to 6.79 (wt.%), aqueous phase yields between 20.34 and 25.57 (wt.%), solid phase yields (coke) between 33.40 and 43.37 (wt.%), and gas yields from 31.85 to 34.45 (wt.%). The yield of bio-oil shows a smooth exponential increase with temperature. The acidity of bio-oil varied between 12.3 and 257.6 mg KOH/g, decreasing exponentially with temperature, while that of the aqueous phase varied between 17.9 and 118.9 mg KOH/g, showing an exponential decay behavior with temperature and demonstrating that higher temperatures favor not only the yield of bio-oil but also bio-oils with lower acidity. For the experiments with KOH activation, the GC-MS of bio-oil identified the presence of hydrocarbons (alkanes, alkenes, cycloalkanes, cycloalkenes, and aromatics) and oxygenates (carboxylic acids, phenols, ketones, and esters). The concentration of hydrocarbons varied between 10.19 and 25.71 (area.%), increasing with temperature, while that of oxygenates varied between 52.69 and 72.15 (area.%), decreasing with temperature. For the experiments with constant temperature, the concentrations of hydrocarbons in bio-oil increased exponentially with molarity, while those of oxygenates decreased exponentially, showing that higher molarities favor the formation of hydrocarbons in bio-oil. The antioxidant activity of bio-oils decreases with increasing temperature, as the content of phenolic compounds decreases, and it decreases with increasing KOH molarity, as higher molarities favor the formation of hydrocarbons. Finally, it can be concluded that chemical activation of açaí seeds with KOH favors not only the yield of bio-oil but also the content of hydrocarbons. The study of process ","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"18 5","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139441538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
K. Chakarova, N. Drenchev, M. Mihaylov, K. Hadjiivanov
The interaction between O2 and reduced ceria nanocubes was mainly investigated using FTIR spectroscopy. Nanorods and nanoparticles were also studied for comparison. Adsorption of O2 at 100 K on unreduced ceria produces only O2 molecularly adsorbed on Ce4+ sites. The Ce3+ cations on ceria reduced by H2 at 773 K were monitored using the 2F5/2 → 2F7/2 electronic transition band at 2133–2095 cm−1. This band possesses a fine structure well resolved at 100 K. The positions of the individual components depend on the Ce3+ environment, including the presence of nearby species such as OH groups. Even at 100 K, adsorption of O2 on reduced ceria leads to fast oxidation of about half of the Ce3+ cations, including all Ce3+ sites bound to OH groups and carbonates, and the simultaneous formation of superoxo (O2−) and peroxo (O22−) species. The remaining Ce3+ sites disappear upon heating up to 348 K. At higher temperatures, the peroxo species decompose directly, yielding lattice oxygen. Superoxides are converted to hydroperoxides, which then decompose into terminal OH groups. Reduced samples evacuated at T < 773 K contain sorbed H2. Part of this hydrogen is also fast oxidized even at 100 K.
傅立叶变换红外光谱主要研究了氧气与还原铈纳米立方体之间的相互作用。此外，还对纳米棒和纳米颗粒进行了比较研究。在 100 K 时，未还原铈上吸附的 O2 只在 Ce4+ 位点上产生分子吸附的 O2。通过 2133-2095 cm-1 处的 2F5/2 → 2F7/2 电子转变带，对 773 K 下被 H2 还原的铈上的 Ce3+ 阳离子进行了监测。各个成分的位置取决于 Ce3+ 环境，包括附近物种（如 OH 基团）的存在。即使在 100 K 时，还原铈上吸附的 O2 也会导致大约一半的 Ce3+ 阳离子快速氧化，包括与 OH 基团和碳酸盐结合的所有 Ce3+ 位点，并同时形成超氧（O2-）和过氧（O22-）物种。在更高温度下，过氧化物直接分解，生成晶格氧。过氧化物转化为氢过氧化物，然后分解为末端羟基。在温度小于 773 K 时抽空的还原样品含有吸附的 H2。其中部分氢即使在 100 K 时也会被快速氧化。
{"title":"Interaction of O2 with Reduced Ceria Nanoparticles at 100–400 K: Fast Oxidation of Ce3+ Ions and Dissolved H2","authors":"K. Chakarova, N. Drenchev, M. Mihaylov, K. Hadjiivanov","doi":"10.3390/catal14010045","DOIUrl":"https://doi.org/10.3390/catal14010045","url":null,"abstract":"The interaction between O2 and reduced ceria nanocubes was mainly investigated using FTIR spectroscopy. Nanorods and nanoparticles were also studied for comparison. Adsorption of O2 at 100 K on unreduced ceria produces only O2 molecularly adsorbed on Ce4+ sites. The Ce3+ cations on ceria reduced by H2 at 773 K were monitored using the 2F5/2 → 2F7/2 electronic transition band at 2133–2095 cm−1. This band possesses a fine structure well resolved at 100 K. The positions of the individual components depend on the Ce3+ environment, including the presence of nearby species such as OH groups. Even at 100 K, adsorption of O2 on reduced ceria leads to fast oxidation of about half of the Ce3+ cations, including all Ce3+ sites bound to OH groups and carbonates, and the simultaneous formation of superoxo (O2−) and peroxo (O22−) species. The remaining Ce3+ sites disappear upon heating up to 348 K. At higher temperatures, the peroxo species decompose directly, yielding lattice oxygen. Superoxides are converted to hydroperoxides, which then decompose into terminal OH groups. Reduced samples evacuated at T < 773 K contain sorbed H2. Part of this hydrogen is also fast oxidized even at 100 K.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"1 5","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139443653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
M. N. Subramaniam, Jiaojiao Zheng, Zhentao Wu, Pei Sean Goh, Guangru Zhang
Researchers are actively pursuing the development of highly functional photocatalyst materials using environmentally friendly and sustainable resources. In this study, wheat straw biochar (BC), a by-product of biomass pyrolysis, was explored as a green, porous substrate and a carbon-based sensitizer to activate Fe-based photocatalysts under visible light. The research also delved into the impact of doping copper (Cu), chromium (Cr), and zinc (Zn) to enhance the photocatalytic activity of BC-Fe-based catalysts for the removal of methylene orange (MO) from water. Characterization results revealed a more than twofold increase in surface area and greater porosity, contributing to improved radical generation. BC demonstrated its dual functionality as a high surface area substrate and an electron sink, facilitating multistep electron movement and enhancing the photoactivity of the composite catalyst. Photodegradation experiments indicated that the combination of BC with Fe and Zn exhibited the highest performance, removing over 80% of MO within 120 min. Parametric studies highlighted the preference for an alkali pH, and the photocatalyst demonstrated efficient performance up to 30 ppm of dye. Radical scavenging experiments identified •OH and h+ as the most generated radicals. This study establishes that the green and sustainable BC holds promise as a material in the quest for more sustainable photocatalysts.
{"title":"Visible Light-Driven Organic Pollutant Removal Using Fe-Based Photocatalysts Supported by Wheat Straw Biochar","authors":"M. N. Subramaniam, Jiaojiao Zheng, Zhentao Wu, Pei Sean Goh, Guangru Zhang","doi":"10.3390/catal14010043","DOIUrl":"https://doi.org/10.3390/catal14010043","url":null,"abstract":"Researchers are actively pursuing the development of highly functional photocatalyst materials using environmentally friendly and sustainable resources. In this study, wheat straw biochar (BC), a by-product of biomass pyrolysis, was explored as a green, porous substrate and a carbon-based sensitizer to activate Fe-based photocatalysts under visible light. The research also delved into the impact of doping copper (Cu), chromium (Cr), and zinc (Zn) to enhance the photocatalytic activity of BC-Fe-based catalysts for the removal of methylene orange (MO) from water. Characterization results revealed a more than twofold increase in surface area and greater porosity, contributing to improved radical generation. BC demonstrated its dual functionality as a high surface area substrate and an electron sink, facilitating multistep electron movement and enhancing the photoactivity of the composite catalyst. Photodegradation experiments indicated that the combination of BC with Fe and Zn exhibited the highest performance, removing over 80% of MO within 120 min. Parametric studies highlighted the preference for an alkali pH, and the photocatalyst demonstrated efficient performance up to 30 ppm of dye. Radical scavenging experiments identified •OH and h+ as the most generated radicals. This study establishes that the green and sustainable BC holds promise as a material in the quest for more sustainable photocatalysts.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"51 5","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139447955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ahmed T. Mosleh, Fatemah F. Al-Harbi, Soumaya M. Gouadria, S. Zyoud, H. Zahran, Mai S. A. Hussien, I. S. Yahia
Historically, the photocatalytic efficacy of graphitic carbon nitride (g-C3N4) has been constrained by a rapid charge recombination rate and restricted sensitivity to visible light. To overcome these limitations and enhance the performance of g-C3N4, the strategic formation of heterojunctions with semiconductor materials is deemed the optimal approach. The present study employed a facile sonication-assisted pyrolysis method to synthesize a g-C3N4@ZrO2 nanocomposite photocatalyst. This hybrid material was characterized extensively using a comprehensive suite of analytical techniques, including XRD, SEM, EDX, FTIR, and UV-Vis DRS. A comparative analysis of photocatalytic applications under identical conditions was conducted for all synthesized materials, wherein they were subjected to UVc light irradiation. The photocatalytic degradation of various dye models, such as MB, EY, and a combination of dyes, was assessed using the prepared nanocomposites. The g-C3N4@ZrO2 photocatalysts showcased superior photocatalytic performance, with a particular variant, g-CNZ6, exhibiting remarkable activity. With a bandgap energy of 2.57 eV, g-CNZ6 achieved impressive degradation efficiencies of 96.5% for MB and 95.6% for EY within 40 min. Following previous studies, the superoxide radical anions (O2−. and h+) were largely accountable for the degradation of MB. Therefore, the observed efficacy of the g-C3N4@ZrO2 nanocomposite photocatalyst can be attributed to the increased generation of these reactive species.
{"title":"Photodegradation of Wastewater Containing Organic Dyes Using Modified G-C3N4-Doped ZrO2 Nanostructures: Towards Safe Water for Human Beings","authors":"Ahmed T. Mosleh, Fatemah F. Al-Harbi, Soumaya M. Gouadria, S. Zyoud, H. Zahran, Mai S. A. Hussien, I. S. Yahia","doi":"10.3390/catal14010042","DOIUrl":"https://doi.org/10.3390/catal14010042","url":null,"abstract":"Historically, the photocatalytic efficacy of graphitic carbon nitride (g-C3N4) has been constrained by a rapid charge recombination rate and restricted sensitivity to visible light. To overcome these limitations and enhance the performance of g-C3N4, the strategic formation of heterojunctions with semiconductor materials is deemed the optimal approach. The present study employed a facile sonication-assisted pyrolysis method to synthesize a g-C3N4@ZrO2 nanocomposite photocatalyst. This hybrid material was characterized extensively using a comprehensive suite of analytical techniques, including XRD, SEM, EDX, FTIR, and UV-Vis DRS. A comparative analysis of photocatalytic applications under identical conditions was conducted for all synthesized materials, wherein they were subjected to UVc light irradiation. The photocatalytic degradation of various dye models, such as MB, EY, and a combination of dyes, was assessed using the prepared nanocomposites. The g-C3N4@ZrO2 photocatalysts showcased superior photocatalytic performance, with a particular variant, g-CNZ6, exhibiting remarkable activity. With a bandgap energy of 2.57 eV, g-CNZ6 achieved impressive degradation efficiencies of 96.5% for MB and 95.6% for EY within 40 min. Following previous studies, the superoxide radical anions (O2−. and h+) were largely accountable for the degradation of MB. Therefore, the observed efficacy of the g-C3N4@ZrO2 nanocomposite photocatalyst can be attributed to the increased generation of these reactive species.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"24 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139448659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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