Understanding the behavior of noble-metal catalysts is a key point of catalysis research aimed at reducing the environmental and economic costs associated with the increased use of automobiles. In this study, the atomic-behaviors of Ru and Pd atoms in PdRu solid-solution nanoparticles (NPs) supported on CeO2-ZrO2 (CZ) as a Rh-free three-way catalyst in a modeled three-way catalytic reaction (TWCR) were elucidated using a gas conversion analysis, transmission electron microscopy, and in-situ X-ray absorption fine structure spectroscopy. We found that the PdRu NPs enlarged by the annealing effect separated a smaller grain size with the Pd-rich and Ru-rich phase under TWCR. Most of the oxidation and reduction reactions under the modeled TWCR occurred on the Ru. However, the Pd metals acted as a major role of the reduction of NO gas and oxidation of CO and C3H6 gas. Ru atoms just is a minor role during the modeled TWCR. This study demonstrates the potential of PdRu NPs as a three-way catalyst and reveals the atomic-behavior and catalytic role under the modeled TWCR.
{"title":"Atomic behaviors in PdRu solid-solution nanoparticles on CeO2-ZrO2 support for the three-way catalytic reaction","authors":"Okkyun Seo , Akhil Tayal , Jaemyung Kim , Kohei Kusada , Tomokazu Yamamoto , Jiayi Tang , Satoshi Hiroi , Chulho Song , Katsutoshi Sato , Katsutoshi Nagaoka , Masaaki Haneda , Kazuo Kato , Syo Matsumura , Hiroshi Kitagawa , Osami Sakata","doi":"10.1016/j.mtcata.2024.100078","DOIUrl":"10.1016/j.mtcata.2024.100078","url":null,"abstract":"<div><div>Understanding the behavior of noble-metal catalysts is a key point of catalysis research aimed at reducing the environmental and economic costs associated with the increased use of automobiles. In this study, the atomic-behaviors of Ru and Pd atoms in PdRu solid-solution nanoparticles (NPs) supported on CeO<sub>2</sub>-ZrO<sub>2</sub> (CZ) as a Rh-free three-way catalyst in a modeled three-way catalytic reaction (TWCR) were elucidated using a gas conversion analysis, transmission electron microscopy, and <em>in</em>-<em>situ</em> X-ray absorption fine structure spectroscopy. We found that the PdRu NPs enlarged by the annealing effect separated a smaller grain size with the Pd-rich and Ru-rich phase under TWCR. Most of the oxidation and reduction reactions under the modeled TWCR occurred on the Ru. However, the Pd metals acted as a major role of the reduction of NO gas and oxidation of CO and C<sub>3</sub>H<sub>6</sub> gas. Ru atoms just is a minor role during the modeled TWCR. This study demonstrates the potential of PdRu NPs as a three-way catalyst and reveals the atomic-behavior and catalytic role under the modeled TWCR.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100078"},"PeriodicalIF":0.0,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142746480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The purpose of this study is to develop a visible light responsive photocatalyst that can remove such environmental pollutants as polysulfide anions and simultaneously generate clean hydrogen energy. An environmentally friendly copper indium sulfide (CuInS2, CIS) nano-colloid was synthesized in aqueous medium for the design of such a photocatalyst. Characterization of the hydrophilic CIS with different In/Cu ratios were studied by XRD, Raman, UV-Vis, photoluminescence spectroscopy. These results showed that the long-lived photoexcited electrons in the CIS with higher In/Cu ratio can be expected to achieve efficient interaction with the reactant molecules. On the photocatalytic activity of CIS, the effect of such various supports as TiO2, and In/Cu ratio of CIS on the reaction promotion was examined. The CIS deposited TiO2 (CIS-TiO2) showed higher photocatalytic activity than bulk CIS, and the indium sulfide-richer CIS-TiO2 showed better performance. The indium sulfide moiety participates in the compensation of the defect sites in the CIS as well as the interaction between In-rich CIS and TiO2 can achieve effective charge carrier separation. This is the first report finding that the indium-richer CuInS2 plays an important role in an improvement of the photocatalytic activity.
{"title":"Effect of the indium sulfide phase in CuInS2-TiO2 photocatalysts to boost hydrogen evolution by water splitting","authors":"Mizuki Inada , Shizuki Yase , Atsune Tada , Takuma Yamane , Yuki Miyaji , Masanari Hirahara , Yoshiyuki Harada , Syuji Fujii , Takashi Fukushima , Satoru Dohshi , Shinya Higashimoto","doi":"10.1016/j.mtcata.2024.100080","DOIUrl":"10.1016/j.mtcata.2024.100080","url":null,"abstract":"<div><div>The purpose of this study is to develop a visible light responsive photocatalyst that can remove such environmental pollutants as polysulfide anions and simultaneously generate clean hydrogen energy. An environmentally friendly copper indium sulfide (CuInS<sub>2</sub>, CIS) nano-colloid was synthesized in aqueous medium for the design of such a photocatalyst. Characterization of the hydrophilic CIS with different In/Cu ratios were studied by XRD, Raman, UV-Vis, photoluminescence spectroscopy. These results showed that the long-lived photoexcited electrons in the CIS with higher In/Cu ratio can be expected to achieve efficient interaction with the reactant molecules. On the photocatalytic activity of CIS, the effect of such various supports as TiO<sub>2</sub>, and In/Cu ratio of CIS on the reaction promotion was examined. The CIS deposited TiO<sub>2</sub> (CIS-TiO<sub>2</sub>) showed higher photocatalytic activity than bulk CIS, and the indium sulfide-richer CIS-TiO<sub>2</sub> showed better performance. The indium sulfide moiety participates in the compensation of the defect sites in the CIS as well as the interaction between In-rich CIS and TiO<sub>2</sub> can achieve effective charge carrier separation. This is the first report finding that the indium-richer CuInS<sub>2</sub> plays an important role in an improvement of the photocatalytic activity.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100080"},"PeriodicalIF":0.0,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143137084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.mtcata.2024.100077
Arsh Ismaili, Gurwinder Singh, CI Sathish, Kavitha Ramadass, Vinay Naral, Stalin Joseph, Mercy Benzigar, Muhammad Ibrar Ahmed, Ajayan Vinu
Mesoporous materials are flourishing across every major research discipline, including carbon capture and conversion, energy storage, biomedical, photocatalysis, optics, and magnetics, and their promising potential has led to a flurry of publications. Among these applications, CO2 conversion using porous heterogeneous catalysts such as zeolites, clays, and mesoporous materials gained much attention in recent years as it has the potential to offer a solution for global warming. Although various porous catalysts have been used for CO2 conversion, mesoporous materials are particularly interesting owing to their large specific surface area, pore volume and pore diameter. These properties can be effectively utilized for creating unique catalytically active sites by loading metal or metal oxide species with high dispersion which are highly critical for efficient CO2 conversion. There have also been a significant number of reports on the direct use of mesoporous metal oxides, sulfides and/or phosphides, which exhibit appealing results for CO2 conversion as these inherently contain metal sites, and mesoporosity addition to them is an added advantage. Their continuous evolution warrants more sophisticated research to unveil their hidden properties by engaging in highly advanced characterization. The major emphasis of this review is to discuss various types of mesoporous materials mentioned above and their functionalized derivatives for CO2 conversion to mainly C1 products. The diverse range of mesoporous materials covered in this review will provide the readers with the opportunity to delve into their specific properties that control the efficiency of CO2 conversion.
介孔材料在碳捕获与转化、能量存储、生物医学、光催化、光学和磁学等各个主要研究学科中都得到了蓬勃发展，其巨大潜力已引发大量论文发表。在这些应用中，使用多孔异质催化剂（如沸石、粘土和介孔材料）进行二氧化碳转化近年来备受关注，因为它有可能为全球变暖提供解决方案。虽然各种多孔催化剂已被用于二氧化碳转化，但介孔材料因其较大的比表面积、孔体积和孔直径而尤其引人关注。可以有效利用这些特性，通过装载高分散度的金属或金属氧化物来创建独特的催化活性位点，这对于高效的二氧化碳转化非常关键。此外，还有大量关于直接使用介孔金属氧化物、硫化物和/或磷化物的报道，由于这些物质本身含有金属位点，因此在二氧化碳转化方面表现出令人满意的效果，而添加介孔也是一个额外的优势。它们的不断发展需要进行更复杂的研究，通过高度先进的表征揭示其隐藏的特性。本综述的主要重点是讨论上述各种类型的介孔材料及其功能化衍生物，用于将 CO2 转化为主要是 C1 产物。本综述中涉及的各种介孔材料将为读者提供机会，深入探讨它们控制二氧化碳转化效率的具体特性。
{"title":"Recent developments in functionalized mesoporous materials for CO2 conversion","authors":"Arsh Ismaili, Gurwinder Singh, CI Sathish, Kavitha Ramadass, Vinay Naral, Stalin Joseph, Mercy Benzigar, Muhammad Ibrar Ahmed, Ajayan Vinu","doi":"10.1016/j.mtcata.2024.100077","DOIUrl":"10.1016/j.mtcata.2024.100077","url":null,"abstract":"<div><div>Mesoporous materials are flourishing across every major research discipline, including carbon capture and conversion, energy storage, biomedical, photocatalysis, optics, and magnetics, and their promising potential has led to a flurry of publications. Among these applications, CO<sub>2</sub> conversion using porous heterogeneous catalysts such as zeolites, clays, and mesoporous materials gained much attention in recent years as it has the potential to offer a solution for global warming. Although various porous catalysts have been used for CO<sub>2</sub> conversion, mesoporous materials are particularly interesting owing to their large specific surface area, pore volume and pore diameter. These properties can be effectively utilized for creating unique catalytically active sites by loading metal or metal oxide species with high dispersion which are highly critical for efficient CO<sub>2</sub> conversion. There have also been a significant number of reports on the direct use of mesoporous metal oxides, sulfides and/or phosphides, which exhibit appealing results for CO<sub>2</sub> conversion as these inherently contain metal sites, and mesoporosity addition to them is an added advantage. Their continuous evolution warrants more sophisticated research to unveil their hidden properties by engaging in highly advanced characterization. The major emphasis of this review is to discuss various types of mesoporous materials mentioned above and their functionalized derivatives for CO<sub>2</sub> conversion to mainly C1 products. The diverse range of mesoporous materials covered in this review will provide the readers with the opportunity to delve into their specific properties that control the efficiency of CO<sub>2</sub> conversion.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100077"},"PeriodicalIF":0.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142724113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.mtcata.2024.100075
Julio C. Fernandes P. Brito , Geo Paul , Claudio Cassino , Ivana Miletto , Leonardo Marchese , Enrica Gianotti
Bi-functional catalysts possess various catalytic sites and can catalyze different types of reactions in a single-pot cascade manner. Herein, we report the synthesis and characterization of mono- and bifunctional silica-based mesoporous hybrid catalysts involving acid and base active sites. The ability for cooperative catalysis has been investigated using a multi-technique approach involving powder X-ray diffraction, FT-IR, and multinuclear MAS NMR spectroscopy, as well as thermogravimetric analysis. To elucidate the nature and strength of multifunctional catalytic sites, different types of probe molecules were employed and studied using spectroscopic techniques. The results show that the activity of the mesoporous surface-grafted acid and/or base sites is directly related to the intimacy criterion, the separation between the different types of catalytic sites. The presence or absence of mutual interactions between the different catalytic sites dictates the selectivity and yield of the reactions.
双功能催化剂具有不同的催化位点，能以单锅级联方式催化不同类型的反应。在此，我们报告了涉及酸和碱活性位点的单功能和双功能硅基介孔杂化催化剂的合成和表征。我们采用粉末 X 射线衍射、傅立叶变换红外光谱、多核 MAS NMR 光谱以及热重分析等多技术方法，对其协同催化能力进行了研究。为了阐明多功能催化位点的性质和强度，采用了不同类型的探针分子，并利用光谱技术对其进行了研究。结果表明，介孔表面接枝酸和/或碱位点的活性与亲和性标准，即不同类型催化位点之间的分离度直接相关。不同催化位点之间是否存在相互作用决定了反应的选择性和产率。
{"title":"Integrated in situ spectroscopic characterization of bi-functional nanoporous hybrid catalysts","authors":"Julio C. Fernandes P. Brito , Geo Paul , Claudio Cassino , Ivana Miletto , Leonardo Marchese , Enrica Gianotti","doi":"10.1016/j.mtcata.2024.100075","DOIUrl":"10.1016/j.mtcata.2024.100075","url":null,"abstract":"<div><div>Bi-functional catalysts possess various catalytic sites and can catalyze different types of reactions in a single-pot cascade manner. Herein, we report the synthesis and characterization of mono- and bifunctional silica-based mesoporous hybrid catalysts involving acid and base active sites. The ability for cooperative catalysis has been investigated using a multi-technique approach involving powder X-ray diffraction, FT-IR, and multinuclear MAS NMR spectroscopy, as well as thermogravimetric analysis. To elucidate the nature and strength of multifunctional catalytic sites, different types of probe molecules were employed and studied using spectroscopic techniques. The results show that the activity of the mesoporous surface-grafted acid and/or base sites is directly related to the intimacy criterion, the separation between the different types of catalytic sites. The presence or absence of mutual interactions between the different catalytic sites dictates the selectivity and yield of the reactions.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100075"},"PeriodicalIF":0.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-06DOI: 10.1016/j.mtcata.2024.100073
Jiayi Deng , Yun Li , Hua Ning , Peilin Qing , Xiantun Huang , Hui Luo , Liang Zhang , Guangxu Li , Cunke Huang , Zhiqiang Lan , Wenzheng Zhou , Jin Guo , Xinhua Wang , Haizhen Liu
Hydrogen can serve as a clean storage medium for large-scale renewable energy due to its characteristics of cleanness, high gravimetric energy density, abundant resources, and flexible applications. However, storing hydrogen in a manner both compactly and safely is still a thorny issue currently. Hydrogen storage in materials provides a feasible solution for such tough issue. Unfortunately, most of the light-weight hydrogen storage materials such as complex metal hydrides (LiBH4, Mg(BH4)2, LiAlH4, NaAlH4, etc.), binary light-weight metal hydrides (MgH2, AlH3, etc.) are currently facing the problems of high thermal stability, slow desorption and absorption kinetics, or poor reversibility. Introduction of catalysts or constructing nanostructures are two of the feasible methods that can efficiently tailor the hydrogen storage properties of the materials. Recently two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides (called MXenes) have shown great development potential as catalysts to regulate the performances of hydrogen storage materials due to their unique electronic properties, layered structures and catalytic activity of the transition metals contained. It is possible to simultaneously nanoconfine and catalyze the hydrogen storage materials by layered MXenes. In this review, the synthesis methods and application situation of MXenes are first briefly introduced. Then, the emphasis is placed on the research progress and recent advances of MXenes as catalysts for regulating the hydrogen storage properties of light materials such as MgH2, AlH3, LiAlH4, NaAlH4, LiBH4, Mg(BH4)2 or multicomponent hydrogen storage composites such as LiBH4−MgH2, MgH2−LiAlH4, LiBH4−Mg(BH4)2, etc. This review demonstrates that MXenes have exhibited very good catalytic activity on the dehydrogenation and rehydrogenation of various hydrogen storage materials. Since there is barely review focused on the various kinds of hydrogen storage materials, this review will close this gap and aims at making a comprehensive discussion and prospect on the studies of MXenes for regulating the properties of various kinds of hydrogen storage materials.
{"title":"MXenes as catalysts for lightweight hydrogen storage materials: A review","authors":"Jiayi Deng , Yun Li , Hua Ning , Peilin Qing , Xiantun Huang , Hui Luo , Liang Zhang , Guangxu Li , Cunke Huang , Zhiqiang Lan , Wenzheng Zhou , Jin Guo , Xinhua Wang , Haizhen Liu","doi":"10.1016/j.mtcata.2024.100073","DOIUrl":"10.1016/j.mtcata.2024.100073","url":null,"abstract":"<div><div>Hydrogen can serve as a clean storage medium for large-scale renewable energy due to its characteristics of cleanness, high gravimetric energy density, abundant resources, and flexible applications. However, storing hydrogen in a manner both compactly and safely is still a thorny issue currently. Hydrogen storage in materials provides a feasible solution for such tough issue. Unfortunately, most of the light-weight hydrogen storage materials such as complex metal hydrides (LiBH<sub>4</sub>, Mg(BH<sub>4</sub>)<sub>2</sub>, LiAlH<sub>4</sub>, NaAlH<sub>4</sub>, etc.), binary light-weight metal hydrides (MgH<sub>2</sub>, AlH<sub>3</sub>, etc.) are currently facing the problems of high thermal stability, slow desorption and absorption kinetics, or poor reversibility. Introduction of catalysts or constructing nanostructures are two of the feasible methods that can efficiently tailor the hydrogen storage properties of the materials. Recently two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides (called MXenes) have shown great development potential as catalysts to regulate the performances of hydrogen storage materials due to their unique electronic properties, layered structures and catalytic activity of the transition metals contained. It is possible to simultaneously nanoconfine and catalyze the hydrogen storage materials by layered MXenes. In this review, the synthesis methods and application situation of MXenes are first briefly introduced. Then, the emphasis is placed on the research progress and recent advances of MXenes as catalysts for regulating the hydrogen storage properties of light materials such as MgH<sub>2</sub>, AlH<sub>3</sub>, LiAlH<sub>4</sub>, NaAlH<sub>4</sub>, LiBH<sub>4</sub>, Mg(BH<sub>4</sub>)<sub>2</sub> or multicomponent hydrogen storage composites such as LiBH<sub>4</sub>−MgH<sub>2</sub>, MgH<sub>2</sub>−LiAlH<sub>4</sub>, LiBH<sub>4</sub>−Mg(BH<sub>4</sub>)<sub>2</sub>, etc. This review demonstrates that MXenes have exhibited very good catalytic activity on the dehydrogenation and rehydrogenation of various hydrogen storage materials. Since there is barely review focused on the various kinds of hydrogen storage materials, this review will close this gap and aims at making a comprehensive discussion and prospect on the studies of MXenes for regulating the properties of various kinds of hydrogen storage materials.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100073"},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-06DOI: 10.1016/j.mtcata.2024.100074
Chaojie Liu , Yongyang Zhu , Anqi Zu , Yike Liu , Zhiyang Zhang , Junjie Guo , Chuo Lian , Muen Zou , Shun Wang
Graphene-based materials with large specific surface area, strong stability and easy adjustability attract considerable attention in the field of hydrogen storage; however, they suffer from poor hydrogen adsorption ability as direct physical adsorbents or limited modification effect as catalytic supporters of chemical hydrides, blamed to tightly stacked layer structure and chemical inertness. Structural engineering and functional decoration on graphene have been proven to be effective strategies for enhancing both physical and chemical hydrogen storage performances, but there is still lack of simple and flexible method to achieve their synergy. Here for the first time, we develop a fluorine-functionalized intercalated graphene with adjustable layer spacing by one-step solvothermal process, using fluorinated organic molecules as both intercalation and function agents. By the virtue of expanded interlayer and high-electronegative fluorine, it shows polarization-enhanced physisorption ability. Moreover, when using it as the supporter for LiBH4, the operation temperature, reaction kinetics and cyclic stability of the whole system are greatly improved, attributed to the intrinsic catalysis of carbonaceous materials and the destabilization induced by fluorine substitution. This work provides new views for structural and functional co-design in graphene derivate, and brings hope for their practical application for hydrogen storage.
{"title":"One-step synthesis of fluorine-functionalized intercalated graphene with adjustable layer spacing for both enhanced physical and chemical hydrogen storage","authors":"Chaojie Liu , Yongyang Zhu , Anqi Zu , Yike Liu , Zhiyang Zhang , Junjie Guo , Chuo Lian , Muen Zou , Shun Wang","doi":"10.1016/j.mtcata.2024.100074","DOIUrl":"10.1016/j.mtcata.2024.100074","url":null,"abstract":"<div><div>Graphene-based materials with large specific surface area, strong stability and easy adjustability attract considerable attention in the field of hydrogen storage; however, they suffer from poor hydrogen adsorption ability as direct physical adsorbents or limited modification effect as catalytic supporters of chemical hydrides, blamed to tightly stacked layer structure and chemical inertness. Structural engineering and functional decoration on graphene have been proven to be effective strategies for enhancing both physical and chemical hydrogen storage performances, but there is still lack of simple and flexible method to achieve their synergy. Here for the first time, we develop a fluorine-functionalized intercalated graphene with adjustable layer spacing by one-step solvothermal process, using fluorinated organic molecules as both intercalation and function agents. By the virtue of expanded interlayer and high-electronegative fluorine, it shows polarization-enhanced physisorption ability. Moreover, when using it as the supporter for LiBH<sub>4</sub>, the operation temperature, reaction kinetics and cyclic stability of the whole system are greatly improved, attributed to the intrinsic catalysis of carbonaceous materials and the destabilization induced by fluorine substitution. This work provides new views for structural and functional co-design in graphene derivate, and brings hope for their practical application for hydrogen storage.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100074"},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-31DOI: 10.1016/j.mtcata.2024.100072
Liyan Chen, Hua Zhang, Kang Xu, Yangsen Xu, Xirui Zhang, Feng Zhu, Fan He, Yu Chen
Ammonia protonic ceramic fuel cells (NH3-PCFCs) are highly appealing energy conversion technologies due to their high efficiency, environmental responsibility, and benign safety features. Nonetheless, progress in NH3-PCFCs is notably impeded by the restricted performance and insufficient lifespan of standard Ni-cermet anodes for ammonia cracking, especially at 550 °C or below. Herein, we report an efficient ammonia cracking layer with a formula of xCo3O4/100-xBaZr0.8Y0.2O3-δ (Co/BZY) (x=10, 20, 30), which is deposited onto the Ni-BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) anode to significantly enhance the NH3 decomposition catalytic activity, thereby improving the performance and durability of NH3-PCFCs at low temperatures. The cells with the addition of a 20Co/80BZY anode catalytic layer (ACL) exhibit low area-specific resistance (ASR) and promising operational longevity under NH3 conditions. At 550°C, the NH3-PCFCs with a 20Co/80BZY ACL exhibit a high peak power density of 0.626 W cm−2 and promising operation durability. This study provides important guidance for constructing high-performance and durable NH3-PCFCs.
{"title":"An active and durable ammonia cracking layer for direct ammonia protonic ceramic fuel cells","authors":"Liyan Chen, Hua Zhang, Kang Xu, Yangsen Xu, Xirui Zhang, Feng Zhu, Fan He, Yu Chen","doi":"10.1016/j.mtcata.2024.100072","DOIUrl":"10.1016/j.mtcata.2024.100072","url":null,"abstract":"<div><div>Ammonia protonic ceramic fuel cells (NH<sub>3</sub>-PCFCs) are highly appealing energy conversion technologies due to their high efficiency, environmental responsibility, and benign safety features. Nonetheless, progress in NH<sub>3</sub>-PCFCs is notably impeded by the restricted performance and insufficient lifespan of standard Ni-cermet anodes for ammonia cracking, especially at 550 °C or below. Herein, we report an efficient ammonia cracking layer with a formula of xCo<sub>3</sub>O<sub>4</sub>/100-xBaZr<sub>0.8</sub>Y<sub>0.2</sub>O<sub>3-δ</sub> (Co/BZY) (x=10, 20, 30), which is deposited onto the Ni-BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3−δ</sub> (BZCYYb) anode to significantly enhance the NH<sub>3</sub> decomposition catalytic activity, thereby improving the performance and durability of NH<sub>3</sub>-PCFCs at low temperatures. The cells with the addition of a 20Co/80BZY anode catalytic layer (ACL) exhibit low area-specific resistance (ASR) and promising operational longevity under NH<sub>3</sub> conditions. At 550°C, the NH<sub>3</sub>-PCFCs with a 20Co/80BZY ACL exhibit a high peak power density of 0.626 W cm<sup>−2</sup> and promising operation durability. This study provides important guidance for constructing high-performance and durable NH<sub>3</sub>-PCFCs.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100072"},"PeriodicalIF":0.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.mtcata.2024.100071
Bingbao Mei , Di Shen , Yao Wei , Jingyuan Ma , Fanfei Sun
The burgeoning field of photothermal catalysis has garnered increasing interest due to the synergistic effects of light and thermal activation. Understanding the intrinsic reaction dynamics and structural evolution during the photothermal catalytic process is crucial for the design of effective photothermal devices and catalysts, as well as for optimizing photothermal performance. In situ X-ray absorption fine structure (XAFS) spectroscopy under operational conditions provides a powerful tool for revealing deep insights into atomic and electronic structures. In this study, we designed and constructed a multifunctional in situ photothermal catalytic cell for XAFS measurement, incorporating gas flow, optical sensing, temperature control, and monitoring. We detail the systematic design of the cell, facilitating the further development of portable and effective devices. To validate the cell’s performance, we used commercial WO3 powder as a reference and obtained high-quality XAFS spectra under the influence of light and heat; we also explored the enhanced charge separation efficiency and the consequent improvement in reaction kinetics due to light irradiation. This study underscores the critical role of in situ cells in operational settings and offers a novel perspective on the mechanisms underlying photothermal reactions.
{"title":"In situ photothermal catalytic cell for X-ray absorption fine structure spectroscopy measurement","authors":"Bingbao Mei , Di Shen , Yao Wei , Jingyuan Ma , Fanfei Sun","doi":"10.1016/j.mtcata.2024.100071","DOIUrl":"10.1016/j.mtcata.2024.100071","url":null,"abstract":"<div><div>The burgeoning field of photothermal catalysis has garnered increasing interest due to the synergistic effects of light and thermal activation. Understanding the intrinsic reaction dynamics and structural evolution during the photothermal catalytic process is crucial for the design of effective photothermal devices and catalysts, as well as for optimizing photothermal performance. <em>In situ</em> X-ray absorption fine structure (XAFS) spectroscopy under operational conditions provides a powerful tool for revealing deep insights into atomic and electronic structures. In this study, we designed and constructed a multifunctional <em>in situ</em> photothermal catalytic cell for XAFS measurement, incorporating gas flow, optical sensing, temperature control, and monitoring. We detail the systematic design of the cell, facilitating the further development of portable and effective devices. To validate the cell’s performance, we used commercial WO<sub>3</sub> powder as a reference and obtained high-quality XAFS spectra under the influence of light and heat; we also explored the enhanced charge separation efficiency and the consequent improvement in reaction kinetics due to light irradiation. This study underscores the critical role of <em>in situ</em> cells in operational settings and offers a novel perspective on the mechanisms underlying photothermal reactions.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100071"},"PeriodicalIF":0.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142537988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-23DOI: 10.1016/j.mtcata.2024.100070
Santhanamoorthi Nachimuthu, Chen-Wei Yeh, Chi-You Liu, Mao-Sheng Su, Jyh-Chiang Jiang
Although inspiration from copper-based natural enzymes has shown promise in improving catalyst design for methane-to-methanol (MTM) oxidation, high productivity, and selectivity under mild conditions remain a significant challenge. This study constructs the dinuclear copper (Cu2) species stabilized within the metal-organic framework (MOF), MIL-53(Al), containing Cu as efficient catalytic sites and explores the ability of different oxidants (O2, N2O, and H2O2) to oxidize Cu2 into the dicopper-oxo (Cu2O2) species using density functional theory (DFT) calculations. Our results indicate the kinetic and thermodynamic favorability of Cu2O2 species formation using O2 as an oxidant within the MIL-53(Al) framework. Furthermore, the thermal stability of Cu2O2/MIL-53(Al) has been verified via ab initio molecular dynamics (AIMD) calculations. The kinetics of the complete MTM oxidation cycle over Cu2O2/MIL-53(Al) have been studied using both DFT and microkinetic simulation methods. The present study predicts that the C-H activation on the Cu2O2/MIL-53(Al) has a low free energy barrier (0.77 eV) and that the high stability of CH3 and its very low free energy barrier in the C-O coupling step favors the methanol formation over the formaldehyde. More importantly, Cu2O2/MIL-53(Al) exhibits high methanol selectivity owing to the inhibition of CH3 dehydrogenation and low methanol desorption energy (0.21 eV). Microkinetic simulations confirm the methanol production under relatively mild reaction conditions (200–280 K and 1 bar). This work provides insights into the feasibility of selective MTM oxidation over this family of MOF under mild conditions.
{"title":"Exploring complete catalytic cycle of methane oxidation to methanol on Cu2O2 stabilized within MIL-53(Al) framework: A combined DFT and microkinetic study","authors":"Santhanamoorthi Nachimuthu, Chen-Wei Yeh, Chi-You Liu, Mao-Sheng Su, Jyh-Chiang Jiang","doi":"10.1016/j.mtcata.2024.100070","DOIUrl":"10.1016/j.mtcata.2024.100070","url":null,"abstract":"<div><div>Although inspiration from copper-based natural enzymes has shown promise in improving catalyst design for methane-to-methanol (MTM) oxidation, high productivity, and selectivity under mild conditions remain a significant challenge. This study constructs the dinuclear copper (Cu<sub>2</sub>) species stabilized within the metal-organic framework (MOF), MIL-53(Al), containing Cu as efficient catalytic sites and explores the ability of different oxidants (O<sub>2</sub>, N<sub>2</sub>O, and H<sub>2</sub>O<sub>2</sub>) to oxidize Cu<sub>2</sub> into the dicopper-oxo (Cu<sub>2</sub>O<sub>2</sub>) species using density functional theory (DFT) calculations. Our results indicate the kinetic and thermodynamic favorability of Cu<sub>2</sub>O<sub>2</sub> species formation using O<sub>2</sub> as an oxidant within the MIL-53(Al) framework. Furthermore, the thermal stability of Cu<sub>2</sub>O<sub>2</sub>/MIL-53(Al) has been verified via ab initio molecular dynamics (AIMD) calculations. The kinetics of the complete MTM oxidation cycle over Cu<sub>2</sub>O<sub>2</sub>/MIL-53(Al) have been studied using both DFT and microkinetic simulation methods. The present study predicts that the C-H activation on the Cu<sub>2</sub>O<sub>2</sub>/MIL-53(Al) has a low free energy barrier (0.77 eV) and that the high stability of CH<sub>3</sub> and its very low free energy barrier in the C-O coupling step favors the methanol formation over the formaldehyde. More importantly, Cu<sub>2</sub>O<sub>2</sub>/MIL-53(Al) exhibits high methanol selectivity owing to the inhibition of CH<sub>3</sub> dehydrogenation and low methanol desorption energy (0.21 eV). Microkinetic simulations confirm the methanol production under relatively mild reaction conditions (200–280 K and 1 bar). This work provides insights into the feasibility of selective MTM oxidation over this family of MOF under mild conditions.</div></div>","PeriodicalId":100892,"journal":{"name":"Materials Today Catalysis","volume":"7 ","pages":"Article 100070"},"PeriodicalIF":0.0,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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