Bifunctional Catalysts Synthesized from Hierarchical Materials and Highly Dispersed Metallic Particles: A New Approach
2024; American Chemical Society; Volume: 10; Issue: 10 Linguagem: Inglês
10.1021/acscentsci.4c01486
ISSN2374-7951
AutoresJuan Antonio Cecilia, Antonio Manuel Pérez-Merchán, Benjamín Torres-Olea,
Tópico(s)Catalysis and Hydrodesulfurization Studies
ResumoInfoMetricsFiguresRef. ACS Central ScienceASAPArticle This publication is Open Access under the license indicated. Learn More CiteCitationCitation and abstractCitation and referencesMore citation options ShareShare onFacebookX (Twitter)WeChatLinkedInRedditEmailJump toExpandCollapse First ReactionsOctober 11, 2024Bifunctional Catalysts Synthesized from Hierarchical Materials and Highly Dispersed Metallic Particles: A New ApproachClick to copy article linkArticle link copied!Bifunctional catalysts were synthesized from etching, transformation, and reduction processes, obtaining highly dispersed metal particles on zeolite.Juan Antonio Cecilia*Juan Antonio CeciliaDepartamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, SpainInstituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, Spain*Email: [email protected]More by Juan Antonio Ceciliahttps://orcid.org/0000-0001-5742-4822Antonio M. Pérez-MerchánAntonio M. Pérez-MerchánDepartamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, SpainInstituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, SpainMore by Antonio M. Pérez-MerchánBenjamín Torres-OleaBenjamín Torres-OleaDepartamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, SpainInstituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, SpainMore by Benjamín Torres-OleaOpen PDFACS Central ScienceCite this: ACS Cent. Sci. 2024, XXXX, XXX, XXX-XXXClick to copy citationCitation copied!https://pubs.acs.org/doi/10.1021/acscentsci.4c01486https://doi.org/10.1021/acscentsci.4c01486Published October 11, 2024 Publication History Published online 11 October 2024newsPublished 2024 by American Chemical Society. This publication is licensed under CC-BY 4.0 . License Summary*You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:Creative Commons (CC): This is a Creative Commons license.Attribution (BY): Credit must be given to the creator.View full license*DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. This publication is licensed underCC-BY 4.0 . License Summary*You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: Creative Commons (CC): This is a Creative Commons license. Attribution (BY): Credit must be given to the creator.View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. License Summary*You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: Creative Commons (CC): This is a Creative Commons license. Attribution (BY): Credit must be given to the creator. View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. License Summary*You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: Creative Commons (CC): This is a Creative Commons license. Attribution (BY): Credit must be given to the creator. View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. ACS PublicationsPublished 2024 by American Chemical SocietySubjectswhat are subjectsArticle subjects are automatically applied from the ACS Subject Taxonomy and describe the scientific concepts and themes of the article.CatalystsCatalytic reactionsMetal nanoparticlesNanoparticlesRedox reactionsThroughout the 20th century, the field of catalysis has developed enormously due to scientific and industrial advances. (1) As a result, the design of catalysts has been optimized to obtain maximum yields under milder conditions. The first catalytic studies were carried out in gaseous or liquid media, where a substance was added to accelerate or inhibit a chemical process. More recently, the focus has shifted to the dispersion of the active phase, aiming to increase the catalytically active surface area, reduce the amount of active phase materials used, and save costs. With the development of microporous and mesoporous materials with ordered structures and modulable pore sizes, (2,3) the next challenge for the scientific community was designing catalysts with pore sizes adapted to the dimensions of the reactant and product molecules in such a way that the active phase could be homogeneously dispersed in the porous material. Traditional methods for dispersing the metallic phase include incipient wetness impregnation and precipitation. However, these methodologies often produce particles with highly heterogeneous crystal sizes, and in most cases, the active phase appears on the external surface of the support material. (4,5) Another recent trend in catalyst synthesis is the development of multifunctional catalysts. These materials are designed to combine catalysts with hydrogenating, acidic, basic, oxidizing, or reducing characteristics, enabling consecutive reactions to occur in a single step, thereby reducing costs. (6,7)Another recent trend in catalyst synthesis is the development of multifunctional catalysts. These materials are designed to combine catalysts with hydrogenating, acidic, basic, oxidizing, or reducing characteristics, enabling consecutive reactions to occur in a single step, thereby reducing costs.Considering the scientific community's interest in this area, Tian et al. developed bifunctional catalysts with both acid and metal centers, as detailed in their paper titled "Construction of metal/zeolite hybrid nanoframe reactors via in situ-kinetics transformations", published in ACS Central Science. (6) The authors focused on achieving small, homogeneous metallic particles within a microporous structure to prevent pore blockage and the resulting diffusion problems caused by metal particles blocking the channels. They selected silicalite-1 nanocrystals, a well-described material, as a template for the synthesis of ZSM-5 nanoframes. This procedure was performed in two steps. In the first step, silicalite-1 templates were etched through the recrystallization of ZSM-5 around silicalite in alkaline media, leading to frame-like nanoarchitectures with hierarchical porosity. In the second step, the ZSM-5 nanoframes were enveloped with layered Ni3Si2O5(OH)4 nanosheets, after which both Ni2+-species and silica were etched in the ZSM-5 nanoframes. Finally, the Ni2+-species were reduced to metallic Ni0 under a H2-flow, resulting in well-dispersed particles across the surface of the ZSM-5 structures, with homogeneous crystals averaging 4.5 nm in size (Figure 1). (6)Figure 1Figure 1. Synthetic mechanism of Ni/SiO2/ZSM-5 nanoframes.High Resolution ImageDownload MS PowerPoint SlideThe authors focused on achieving small, homogeneous metallic particles within a microporous structure to prevent pore blockage and the resulting diffusion problems caused by metal particles blocking the channels.The authors then utilized these metal/zeolite hybrid nanoframes in the hydrodeoxygenation (HDO) of stearic acid to obtain diesel derivatives, although this type of catalyst can be extrapolated to other processes where bifunctional catalysts are required (Figure 2). In this reaction, the presence of acid sites promotes hydroisomerization and hydrocracking, while the metallic sites are responsible for the HDO. (9) The catalytic results indicate that the porosity and acidity of the zeolite, as well as the dispersion of the metallic sites, significantly impact the catalytic behavior for obtaining diesel derivatives, confirming that this synthetic approach is well-suited for designing catalysts with tunable pore sizes and acidity, and highly dispersed metallic phases. (1)Figure 2Figure 2. Reaction scheme for the hydrodeoxygenation of stearic acid.High Resolution ImageDownload MS PowerPoint SlideThe authors then utilized these metal/zeolite hybrid nanoframes in the hydrodeoxygenation (HDO) of stearic acid to obtain diesel derivatives.With this methodology, the Si/Al molar ratio can be modulated, (8) allowing for control over the amount of acid sites in the catalysts. In the same way, this approach can be used to modulate Lewis and Brönsted acid sites by selectively blocking certain acid sites or through dealumination or desilication processes. Such high versatility makes it possible to tailor ZSM-5 nanoframes for a wide range of reactions, such as hydrocracking, hydroalkylation, isomerization, and dehydration, among others. Additionally, the incorporation of metallic species into the ZSM-5 nanoframes promotes the dispersion of small, homogeneous metallic particles. Tian et al. also pointed out that it would be possible to introduce several transition metals, such as Ni, Co, Fe, and even bimetallic phases, all with small, homogeneous crystal sizes. These features highlight the broad versatility of this methodology for synthesizing bifunctional catalysts. (1)Author InformationClick to copy section linkSection link copied!Corresponding AuthorJuan Antonio Cecilia - Departamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, Spain; Instituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, Spain; https://orcid.org/0000-0001-5742-4822; Email: [email protected]AuthorsAntonio M. Pérez-Merchán - Departamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, Spain; Instituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, SpainBenjamín Torres-Olea - Departamento de Química, Inorgánica, Cristalografría y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos s/n, 29017 Málaga, Spain; Instituto de Investigación en Biorrefinerías "I3B", Facultad de Ciencias, Universidad de Jaén, Universidad de Granada, Universidad de Sevilla, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga, SpainReferencesClick to copy section linkSection link copied! This article references 9 other publications. 1Wisniak, J. The history of catalysis. From the beginning to Nobel prizes. Educación Química 2010, 21, 60– 69, DOI: 10.1016/S0187-893X(18)30074-0 Google Scholar1The history of catalysis. From the beginning to Nobel prizesWisniak, JaimeEducacion Quimica (2010), 21 (1), 60-69CODEN: EUQIEM; ISSN:0187-893X. (Facultad de Quimica de la UNAM) Although the effects of catalysis are known from very ancient times, the understanding of the phenomena started only in the 18th century and in due course led to the awarding to two Nobel prizes at the beginning of the 20th century. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXkslyhsb4%253D&md5=cf66002e11b61d22b48cf4ed3f6052712Hosono, N.; Kitagawa, S. Modular design of porous soft materials via self-organization of metal organic cages. Acc. Chem. Res. 2018, 51, 2437– 2446, DOI: 10.1021/acs.accounts.8b00361 Google ScholarThere is no corresponding record for this reference.3Barton, T. J.; Bull, L. M.; Klemperer, W. G.; Loy, D. A.; McEnaney, B.; Misono, M.; Monson, P. A.; Pez, G.; Scherer, G. W.; Vartuli, J. C.; Yaghi, O. M. Tailored porous materials. Chem. Mater. 1999, 11, 2633– 2656, DOI: 10.1021/cm9805929 Google Scholar3Tailored Porous MaterialsBarton, Thomas J.; Bull, Lucy M.; Klemperer, Walter G.; Loy, Douglas A.; McEnaney, Brian; Misono, Makoto; Monson, Peter A.; Pez, Guido; Scherer, George W.; Vartuli, James C.; Yaghi, Omar M.Chemistry of Materials (1999), 11 (10), 2633-2656CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society) A review, with 205 refs., is the product of a study panel convened under the auspices of the United States Department of Energy Council on Materials Research to assess the basic research needs and opportunities in the area of tailored porous materials. Tailoring of porous materials involves not only chem. synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials as fibers, thin films, and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide mol. sieves, porous coordination solids, porous carbons, sol-gel-derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theor. approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXms1Gkur8%253D&md5=d14eaaa7db367cfc92193dd1cdf60f434Cui, X.; Li, W.; Ryabchuk, P.; Junge, K.; Beller, M. Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat. Catal. 2018, 1, 385– 397, DOI: 10.1038/s41929-018-0090-9 Google Scholar4Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalystsCui, Xinjiang; Li, Wu; Ryabchuk, Pavel; Junge, Kathrin; Beller, MatthiasNature Catalysis (2018), 1 (6), 385-397CODEN: NCAACP; ISSN:2520-1158. (Nature Research) A review. In heterogeneous single-metal-site catalysts (HSMSCs) the active metal centers are located individually on a support and are stabilized by neighboring surface atoms such as nitrogen, oxygen or sulfur. Modern characterization techniques allow the identification of these individual metal atoms on a given support, and the resulting materials are often referred as single-atom catalysts. Their electronic properties and catalytic activity are tuned by the interaction between the central metal and the neighboring surface atoms, and their atomically dispersed nature allows for metal utilization of up to 100%. In this way, HSMSCs provide new opportunities for catalysis, and with respect to structure build a bridge between homogeneous and heterogeneous catalysis. Herein, selected publications from 2010 in this area are ed and their perspectives for the near future are highlighted. Where appropriate, comparisons between HSMSCs and homogeneous/heterogeneous counterparts are presented. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFGisbvP&md5=c306f83c74d23bd83fa207eef1efe99a5Jing, W.; Shen, H.; Qin, R.; Wu, Q.; Liu, K.; Zheng, N. Surface and interface coordination chemistry learned from model heterogeneous metal nanocatalysts: From atomically dispersed catalysts to atomically precise clusters. Chem. Rev. 2023, 123, 5948– 6002, DOI: 10.1021/acs.chemrev.2c00569 Google Scholar5Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise ClustersJing, Wentong; Shen, Hui; Qin, Ruixuan; Wu, Qingyuan; Liu, Kunlong; Zheng, NanfengChemical Reviews (Washington, DC, United States) (2023), 123 (9), 5948-6002CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society) A review. The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated surface and interface structures of heterogeneous catalysts make it challenging to identify the mol.-level structure of their active sites and thus precisely control their performance. To address this challenge, atomically dispersed metal catalysts (ADMCs) and ligand-protected atomically precise metal clusters (APMCs) have been emerging as two important classes of model heterogeneous catalysts in recent years, helping to build bridge between homogeneous and heterogeneous catalysis. This review illustrates how the surface and interface coordination chem. of these two types of model catalysts dets. the catalytic performance from multiple dimensions. The section of ADMCs starts with the local coordination structure of metal sites at the metal-support interface, and then focuses on the effects of coordinating atoms, including their basicity and hardness/softness. Studies are also summarized to discuss the cooperativity achieved by dual metal sites and remote effects. In the section of APMCs, the roles of surface ligands and supports in detg. the catalytic activity, selectivity, and stability of APMCs are illustrated. Finally, some personal perspectives on the further development of surface coordination and interface chem. for model heterogeneous metal catalysts are presented. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFyhtrrP&md5=1a7f79ecc12213f87e1edcd926414d216Tian, G.; Chen, G.; Yang, G.; Diao, Z.; Bai, R.; Han, J.; Guan, B.; Yu, J. Construction of metal/zeolite hybrid nanoframe reactors via in situ-kinetics transformations. ACS Cent. Sci. 2024, 10, 1473– 1480, DOI: 10.1021/acscentsci.4c00439 Google ScholarThere is no corresponding record for this reference.7Robinson, A. M.; Hensley, J. E.; Medlin, J. W. Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review. ACS Catal. 2016, 6, 5026– 5043, DOI: 10.1021/acscatal.6b00923 Google Scholar7Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A ReviewRobinson, Allison M.; Hensley, Jesse E.; Medlin, J. WillACS Catalysis (2016), 6 (8), 5026-5043CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society) Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chems. A key route for biomass refining involves the prodn. of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the different types of elementary reaction steps required to deoxygenate biomass-derived compds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compds. for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via mol.-level mechanisms. These studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtVektrbM&md5=b4e8ac2db76176fdd4e1b6a3d94b892f8Lanzafame, P.; Papanikolaou, G.; Perathoner, S.; Centi, G.; Giordano, G.; Migliori, M. Weakly acidic zeolites: A review on uses and relationship between nature of the active sites and catalytic behaviour. Microporous Mesoporous Mater. 2020, 300, 110157, DOI: 10.1016/j.micromeso.2020.110157 Google Scholar8Weakly acidic zeolites: A review on uses and relationship between nature of the active sites and catalytic behaviourLanzafame, P.; Papanikolaou, G.; Perathoner, S.; Centi, G.; Giordano, G.; Migliori, M.Microporous and Mesoporous Materials (2020), 300 (), 110157CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.) A review. Weakly acidic zeolites play a role in catalytic reactions, esp. for transformation of biomass-derived products, where the control of the selectivity plays a crucial role. This review discusses this topic, having received limited attention in literature, to remark how represent both a scientific and applicative valuable area. The review offers clues for understanding how weak acid sites in zeolites could be an opportunity in some specific cases, but the aim is not to provide a systematic state-of-the-art. Rather, after introducing considerable examples and cases where mild acidity could be important (etherification, esterification, epoxidn. and Beckmann rearrangement) and a discussion of the nature of weak acid sites, related to defects, present in Silicalite and how to control their nature/amt., the discussion is centered on a more in-depth anal. of three case examples: (i) the effect of introduction of T3+ atoms in Silicalite-1, (ii) the creation of mesoporosity in Fe-MFI and (iii) catalysis by ammonium zeolite forms. HMF (5-hydroxymethyl furfural) etherification reaction is a main reaction discussed. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlsVejtr4%253D&md5=4269b7cab60b7e203f3ecc185656c0169Qu, L.; Jiang, X.; Zhang, Z.; Zhang, X. G.; Song, G. Y.; Wang, H. L.; Yuan, Y. P.; Chang, Y. L. A review of hydrodeoxygenation of bio-oil: model compounds, catalysts, and equipment. Green Chem. 2021, 23, 9348– 9376, DOI: 10.1039/D1GC03183J Google Scholar9A review of hydrodeoxygenation of bio-oil: model compounds, catalysts, and equipmentQu, Lu; Jiang, Xia; Zhang, Zihao; Zhang, Xiang-gang; Song, Guo-yong; Wang, Hua-lin; Yuan, Yuan-ping; Chang, Yu-longGreen Chemistry (2021), 23 (23), 9348-9376CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry) A review. Bio-oils are an important part of the future energy compn. This review primarily focuses on model compds., catalysts, and equipment involved in the hydrodeoxygenation (HDO) of bio-oils. Initially, this article reviews the basic physicochem. properties of bio-oils and introduces different upgrading methods. Among them, HDO can effectively facilitate calorific value and improve the acidity and viscosity of bio-oils. Secondly, the basic HDO reaction pathways and proposed catalytic mechanism of various model compds. are summarized to understand the catalytic behavior and structure-performance relationship of the HDO reaction. Subsequently, we review different catalysts used in actual HDO of bio-oils, some of which lead to excellent stability and improved HDO reactivity. Finally, progress in the development of HDO equipment, including fixed bed and ebullated bed reactors in the pilot stage, is reviewed. This review aims to summarize progress in the utilization of the HDO process and provides useful insights for the efficient practical application of bio-oils. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlCms7jJ&md5=26ced658f30fdfc041fd15592c5a02b0Cited By Click to copy section linkSection link copied!This article has not yet been cited by other publications.Download PDFFiguresReferencesOpen PDF Get e-AlertsGet e-AlertsACS Central ScienceCite this: ACS Cent. Sci. 2024, XXXX, XXX, XXX-XXXClick to copy citationCitation copied!https://doi.org/10.1021/acscentsci.4c01486Published October 11, 2024 Publication History Published online 11 October 2024Published 2024 by American Chemical Society. This publication is licensed under CC-BY 4.0 . License Summary*You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:Creative Commons (CC): This is a Creative Commons license.Attribution (BY): Credit must be given to the creator.View full license*DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. Article Views-Altmetric-Citations-Learn about these metrics closeArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.Recommended Articles FiguresReferencesAbstractHigh Resolution ImageDownload MS PowerPoint SlideFigure 1Figure 1. Synthetic mechanism of Ni/SiO2/ZSM-5 nanoframes.High Resolution ImageDownload MS PowerPoint SlideFigure 2Figure 2. Reaction scheme for the hydrodeoxygenation of stearic acid.High Resolution ImageDownload MS PowerPoint SlideReferences This article references 9 other publications. 1Wisniak, J. The history of catalysis. From the beginning to Nobel prizes. Educación Química 2010, 21, 60– 69, DOI: 10.1016/S0187-893X(18)30074-0 1The history of catalysis. From the beginning to Nobel prizesWisniak, JaimeEducacion Quimica (2010), 21 (1), 60-69CODEN: EUQIEM; ISSN:0187-893X. (Facultad de Quimica de la UNAM) Although the effects of catalysis are known from very ancient times, the understanding of the phenomena started only in the 18th century and in due course led to the awarding to two Nobel prizes at the beginning of the 20th century. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXkslyhsb4%253D&md5=cf66002e11b61d22b48cf4ed3f6052712Hosono, N.; Kitagawa, S. Modular design of porous soft materials via self-organization of metal organic cages. Acc. Chem. Res. 2018, 51, 2437– 2446, DOI: 10.1021/acs.accounts.8b00361 There is no corresponding record for this reference.3Barton, T. J.; Bull, L. M.; Klemperer, W. G.; Loy, D. A.; McEnaney, B.; Misono, M.; Monson, P. A.; Pez, G.; Scherer, G. W.; Vartuli, J. C.; Yaghi, O. M. Tailored porous materials. Chem. Mater. 1999, 11, 2633– 2656, DOI: 10.1021/cm9805929 3Tailored Porous MaterialsBarton, Thomas J.; Bull, Lucy M.; Klemperer, Walter G.; Loy, Douglas A.; McEnaney, Brian; Misono, Makoto; Monson, Peter A.; Pez, Guido; Scherer, George W.; Vartuli, James C.; Yaghi, Omar M.Chemistry of Materials (1999), 11 (10), 2633-2656CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society) A review, with 205 refs., is the product of a study panel convened under the auspices of the United States Department of Energy Council on Materials Research to assess the basic research needs and opportunities in the area of tailored porous materials. Tailoring of porous materials involves not only chem. synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials as fibers, thin films, and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide mol. sieves, porous coordination solids, porous carbons, sol-gel-derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theor. approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXms1Gkur8%253D&md5=d14eaaa7db367cfc92193dd1cdf60f434Cui, X.; Li, W.; Ryabchuk, P.; Junge, K.; Beller, M. Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat. Catal. 2018, 1, 385– 397, DOI: 10.1038/s41929-018-0090-9 4Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalystsCui, Xinjiang; Li, Wu; Ryabchuk, Pavel; Junge, Kathrin; Beller, MatthiasNature Catalysis (2018), 1 (6), 385-397CODEN: NCAACP; ISSN:2520-1158. (Nature Research) A review. In heterogeneous single-metal-site catalysts (HSMSCs) the active metal centers are located individually on a support and are stabilized by neighboring surface atoms such as nitrogen, oxygen or sulfur. Modern characterization techniques allow the identification of these individual metal atoms on a given support, and the resulting materials are often referred as single-atom catalysts. Their electronic properties and catalytic activity are tuned by the interaction between the central metal and the neighboring surface atoms, and their atomically dispersed nature allows for metal utilization of up to 100%. In this way, HSMSCs provide new opportunities for catalysis, and with respect to structure build a bridge between homogeneous and heterogeneous catalysis. Herein, selected publications from 2010 in this area are ed and their perspectives for the near future are highlighted. Where appropriate, comparisons between HSMSCs and homogeneous/heterogeneous counterparts are presented. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtFGisbvP&md5=c306f83c74d23bd83fa207eef1efe99a5Jing, W.; Shen, H.; Qin, R.; Wu, Q.; Liu, K.; Zheng, N. Surface and interface coordination chemistry learned from model heterogeneous metal nanocatalysts: From atomically dispersed catalysts to atomically precise clusters. Chem. Rev. 2023, 123, 5948– 6002, DOI: 10.1021/acs.chemrev.2c00569 5Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise ClustersJing, Wentong; Shen, Hui; Qin, Ruixuan; Wu, Qingyuan; Liu, Kunlong; Zheng, NanfengChemical Reviews (Washington, DC, United States) (2023), 123 (9), 5948-6002CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society) A review. The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated surface and interface structures of heterogeneous catalysts make it challenging to identify the mol.-level structure of their active sites and thus precisely control their performance. To address this challenge, atomically dispersed metal catalysts (ADMCs) and ligand-protected atomically precise metal clusters (APMCs) have been emerging as two important classes of model heterogeneous catalysts in recent years, helping to build bridge between homogeneous and heterogeneous catalysis. This review illustrates how the surface and interface coordination chem. of these two types of model catalysts dets. the catalytic performance from multiple dimensions. The section of ADMCs starts with the local coordination structure of metal sites at the metal-support interface, and then focuses on the effects of coordinating atoms, including their basicity and hardness/softness. Studies are also summarized to discuss the cooperativity achieved by dual metal sites and remote effects. In the section of APMCs, the roles of surface ligands and supports in detg. the catalytic activity, selectivity, and stability of APMCs are illustrated. Finally, some personal perspectives on the further development of surface coordination and interface chem. for model heterogeneous metal catalysts are presented. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFyhtrrP&md5=1a7f79ecc12213f87e1edcd926414d216Tian, G.; Chen, G.; Yang, G.; Diao, Z.; Bai, R.; Han, J.; Guan, B.; Yu, J. Construction of metal/zeolite hybrid nanoframe reactors via in situ-kinetics transformations. ACS Cent. Sci. 2024, 10, 1473– 1480, DOI: 10.1021/acscentsci.4c00439 There is no corresponding record for this reference.7Robinson, A. M.; Hensley, J. E.; Medlin, J. W. Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review. ACS Catal. 2016, 6, 5026– 5043, DOI: 10.1021/acscatal.6b00923 7Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A ReviewRobinson, Allison M.; Hensley, Jesse E.; Medlin, J. WillACS Catalysis (2016), 6 (8), 5026-5043CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society) Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chems. A key route for biomass refining involves the prodn. of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the different types of elementary reaction steps required to deoxygenate biomass-derived compds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compds. for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via mol.-level mechanisms. These studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtVektrbM&md5=b4e8ac2db76176fdd4e1b6a3d94b892f8Lanzafame, P.; Papanikolaou, G.; Perathoner, S.; Centi, G.; Giordano, G.; Migliori, M. Weakly acidic zeolites: A review on uses and relationship between nature of the active sites and catalytic behaviour. Microporous Mesoporous Mater. 2020, 300, 110157, DOI: 10.1016/j.micromeso.2020.110157 8Weakly acidic zeolites: A review on uses and relationship between nature of the active sites and catalytic behaviourLanzafame, P.; Papanikolaou, G.; Perathoner, S.; Centi, G.; Giordano, G.; Migliori, M.Microporous and Mesoporous Materials (2020), 300 (), 110157CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.) A review. Weakly acidic zeolites play a role in catalytic reactions, esp. for transformation of biomass-derived products, where the control of the selectivity plays a crucial role. This review discusses this topic, having received limited attention in literature, to remark how represent both a scientific and applicative valuable area. The review offers clues for understanding how weak acid sites in zeolites could be an opportunity in some specific cases, but the aim is not to provide a systematic state-of-the-art. Rather, after introducing considerable examples and cases where mild acidity could be important (etherification, esterification, epoxidn. and Beckmann rearrangement) and a discussion of the nature of weak acid sites, related to defects, present in Silicalite and how to control their nature/amt., the discussion is centered on a more in-depth anal. of three case examples: (i) the effect of introduction of T3+ atoms in Silicalite-1, (ii) the creation of mesoporosity in Fe-MFI and (iii) catalysis by ammonium zeolite forms. HMF (5-hydroxymethyl furfural) etherification reaction is a main reaction discussed. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlsVejtr4%253D&md5=4269b7cab60b7e203f3ecc185656c0169Qu, L.; Jiang, X.; Zhang, Z.; Zhang, X. G.; Song, G. Y.; Wang, H. L.; Yuan, Y. P.; Chang, Y. L. A review of hydrodeoxygenation of bio-oil: model compounds, catalysts, and equipment. Green Chem. 2021, 23, 9348– 9376, DOI: 10.1039/D1GC03183J 9A review of hydrodeoxygenation of bio-oil: model compounds, catalysts, and equipmentQu, Lu; Jiang, Xia; Zhang, Zihao; Zhang, Xiang-gang; Song, Guo-yong; Wang, Hua-lin; Yuan, Yuan-ping; Chang, Yu-longGreen Chemistry (2021), 23 (23), 9348-9376CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry) A review. Bio-oils are an important part of the future energy compn. This review primarily focuses on model compds., catalysts, and equipment involved in the hydrodeoxygenation (HDO) of bio-oils. Initially, this article reviews the basic physicochem. properties of bio-oils and introduces different upgrading methods. Among them, HDO can effectively facilitate calorific value and improve the acidity and viscosity of bio-oils. Secondly, the basic HDO reaction pathways and proposed catalytic mechanism of various model compds. are summarized to understand the catalytic behavior and structure-performance relationship of the HDO reaction. Subsequently, we review different catalysts used in actual HDO of bio-oils, some of which lead to excellent stability and improved HDO reactivity. Finally, progress in the development of HDO equipment, including fixed bed and ebullated bed reactors in the pilot stage, is reviewed. This review aims to summarize progress in the utilization of the HDO process and provides useful insights for the efficient practical application of bio-oils. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlCms7jJ&md5=26ced658f30fdfc041fd15592c5a02b0
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