Article
Chemistry, Organic
Shuma Sasaki, Jun Kikuchi, Shingo Ito, Naohiko Yoshikai
Summary: In this study, a method for preparing stereodefined enolates by leveraging the stereoselective oxyfunctionalization of unactivated alkynes and their reaction with aldehydes to form γ,δ-unsaturated β-diketones was described.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Fangliang Li, Binli Wang, Xiao Chen, Hongjun Fan, Xueming Yang, Qing Guo
Summary: The study shows that the R-TiO2(100)-(1 x 1) surface exhibits high reactivity and selectivity for aldol condensation of unbranched aldehydes at room temperature. The low energy barriers for enolization and dehydration reactions, along with stable adsorption of intermediates, contribute to the surface's efficiency in forming crotonaldehyde. The exclusive selectivity of (E)-crotonaldehyde formation is attributed to the adsorption configuration of CH3CHO and surface structure of R-TiO2(100)(1 x 1).
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Shashikant A. Kadam, Andrew Hwang, Enrique Iglesia
Summary: This study investigates the effects of non-polar liquids on acetone aldol condensation reactions on TiO2 surfaces. The results show that non-polar liquids enhance reaction rates and selectivity by stabilizing transition states for adsorption and desorption. Additionally, solvation by non-polar liquids prevents the formation of larger oligomers, leading to slower deactivation of the catalyst.
Article
Chemistry, Multidisciplinary
Dariusz Ciez, Aleksandra Palasz, Krzysztof Koziel, Antonii Lutsan, Justyna Kalinowska-Tluscik
Summary: Titanium(iv) enolates of cyclododecanone are used as CH-acidic units in aldol additions, leading to the formation of β-hydroxy carbonyl compounds. The reactions are carried out at low temperatures to minimize dehydration and enone formation. Unlike alkali metal enolates, titanium(iv) enolates of cyclododecanone favor syn-stereoselectivity. The stereoselectivity of the aldolization reaction depends on the size and location of substituents in the aromatic ring of benzaldehydes.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Qiang Deng, Honggen Peng, Zhenzhen Yang, Tao Wang, Jun Wang, Zheling Zeng, Sheng Dai
Summary: Developing a powerful bifunctional catalyst is crucial for achieving future carbon neutrality by reducing energy consumption in the chemical industry. This study synthesizes mesoporous zeolite-encapsulated palladium nanoparticles (Pd@meso-ZSM-5) using emulsification-demulsification and dry-gel transformation methods, which exhibit remarkable catalytic performance in the one-pot multiple tandem reaction of cyclic ketones to bicyclic alkanes. Unlike traditional two-step synthesis routes, Pd@meso-ZSM-5 efficiently produces bicyclic alkanes instead of monocyclic alkanes, due to the sufficient space for large molecular intermediates provided by mesoporosity and the promoting effect of the acid-Pd interface on intermediate conversion.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Ruiyi Yan, Zhaopo Lv, Hongguo Tang, Yinge Bai, Mengyue Li, Yuchao Li
Summary: The study utilized diethylammonium acetate as a catalyst to achieve a high conversion rate of 99.9% from propionaldehyde to methacrolein, with a selectivity of 97.4%. Isotopic tracing experiments and decreasing the reaction temperature were used to propose a possible reaction mechanism.
Review
Chemistry, Physical
Bert Biesemans, Jeriffa De Clercq, Christian V. Stevens, Joris W. Thybaut, Jeroen Lauwaert
Summary: Aminated materials play a crucial role as aldol condensation catalysts, facilitating the reaction through an enamine mechanism. The reaction environment and the addition of small amounts of water are important factors. The development of water tolerant (bio)polymer supported amine catalysts has opened up opportunities for further catalyst development.
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
(2022)
Article
Green & Sustainable Science & Technology
Shanshan Shao, Xinggang Hu, Wenbin Dong, Xiaohua Li, Huiyan Zhang, Rui Xiao, Yixi Cai
Summary: A bifunctional catalyst integrating Aldol condensation and hydrogenation was successfully prepared, achieving an increased yield of targeted alkanes. In the reusability test, the introduction of n-pentane as a solvent proved effective in attenuating the hydration effect.
JOURNAL OF CLEANER PRODUCTION
(2021)
Article
Energy & Fuels
Xiang Tan, Heng Zhang, Hu Li, Song Yang
Summary: By optimizing the combination of different material components, a composite catalyst HPW/UiO-66-NH2 with superior performance in esterification reactions was developed, showcasing the synergistic effect of the combined bifunctional acid species. The activation energy for the esterification reaction was determined to be 31.0 kJ/mol, and the bifunctional composite catalyst exhibited stability and high reusability during consecutive recycles.
Article
Energy & Fuels
Thanatchai Meemanah, Atikhun Chotirattanachote, Junaid Ahmad, Umer Rashid, Chawalit Ngamcharussrivichai
Summary: Herein, furfural, a lignocellulose-derived platform chemical, was converted into a bio-jet fuel precursor via aldol condensation with 2-butanone using strontium and titanium mixed oxides loaded onto mesoporous silica SBA-15. The acid-base properties of the catalysts and the reaction conditions strongly influenced the yield and selectivity of α,β-unsaturated C9 ketone with a branched molecular structure. The optimized catalyst, 20STO(2:1)/SBA15, achieved > 99% furfural conversion and 78.3% C9B yield under specific conditions.
Article
Chemistry, Organic
Shyamal Kanti Bera, Prasenjit Mal
Summary: The study demonstrated the successful synthesis of phenanthridinone derivatives using NBS and NCS as bifunctional reagents under mechanochemical conditions. This approach allowed for the cascaded C-N bond formation and subsequent halogenation reactions, showcasing a potential application of alternative energy sources in chemical transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Mengchao Hou, Fang Li, Aizhong Jia, Yingying Wang, Yanji Wang
Summary: In this study, a series of carbon-based composites with acid-base functions and porous structures were successfully prepared through a simple method. These materials exhibited efficient catalytic performance in the self-condensation of n-butyraldehyde. The introduction of MgO and the in situ transformation facilitated the fabrication of highly dispersed basic sites and acid sites. The synthesized materials possessed a large surface area and rich pores.
REACTION CHEMISTRY & ENGINEERING
(2022)
Article
Energy & Fuels
Marwa M. Naeem, Eslam G. Al-Sakkari, Daria C. Boffito, Eldon R. Rene, Mamdouh A. Gadalla, Fatma H. Ashour
Summary: Sonication and heterogeneous catalysis have been widely studied to enhance biodiesel production. In this study, sonication was used for single-stage biodiesel generation from waste oil catalyzed by KOH/corncob activated carbon. Optimized reaction conditions were determined as 3 wt % catalyst loading, 5 min reaction time, and 18:1 methanol-to-oil molar ratio, resulting in an 88% biodiesel yield without soap formation and meeting ASTM criteria. The combination of ultrasound-assisted heterogeneous catalysis improved overall biodiesel productivity, economic viability, and environmental performance.
Article
Thermodynamics
Hao Wang, Heng Zhou, Qiong Yan, Xu Wu, Heng Zhang
Summary: This study successfully synthesized bifunctional acid superparamagnetic nanospheres and utilized them to convert high acid value Euphorbia lathyris L. oil into biodiesel. The research found that acid sites had important synergistic effects on the biodiesel yield, and the catalyst exhibited excellent stability and repeatability.
ENERGY CONVERSION AND MANAGEMENT
(2023)
Article
Chemistry, Physical
Weiyang Xue, Bin Gu, Huiling Wu, Mengyang Liu, Songbo He, Jingmei Li, Xin Rong, Chenglin Sun
Summary: A batch one-pot cascade approach using a bifunctional Pd/ZrO2 catalyst was developed for the synthesis of 2-alkyl cycloketones, achieving high conversion and yield at mild temperature. The catalyst showed slight deactivation after 10 cycles of reuse, but its performance was completely recovered after an oxidative regeneration.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Physical
Shashikant A. Kadam, Andrew Hwang, Enrique Iglesia
Summary: This study investigates the effects of non-polar liquids on acetone aldol condensation reactions on TiO2 surfaces. The results show that non-polar liquids enhance reaction rates and selectivity by stabilizing transition states for adsorption and desorption. Additionally, solvation by non-polar liquids prevents the formation of larger oligomers, leading to slower deactivation of the catalyst.
Article
Chemistry, Multidisciplinary
Zhaoxia Zhang, Peijie Han, Leisu Li, Xindi Zhang, Xiaojie Cheng, Jingdong Lin, Shaolong Wan, Haifeng Xiong, Yong Wang, Shuai Wang
Summary: The Fenton-type oxidation of lignin derivatives can be carried out with high selectivity for formic acid using a bimetallic Fe-Cu catalyst supported on a ZSM-5 zeolite. The active metal sites in the micropores of the zeolite preferentially adsorb intermediate compounds, suppressing the secondary oxidation of formic acid and resulting in the high selectivity observed.
Article
Chemistry, Physical
Trenton Otto, Xiaoyu Zhou, Stacey I. Zones, Enrique Iglesia
Summary: A synthetic procedure was developed for encapsulating Au nanoparticles within titanium silicalite-1 (TS-1), allowing for the assembly of TS-1 frameworks around Au coordination complexes. Changes to established crystallization procedures for TS-1 led to successful encapsulation of small Au nanoparticles, which showed catalytic activity for propene epoxidation.
JOURNAL OF CATALYSIS
(2022)
Article
Multidisciplinary Sciences
Mingwu Tan, Yanling Yang, Ying Yang, Jiali Chen, Zhaoxia Zhang, Gang Fu, Jingdong Lin, Shaolong Wan, Shuai Wang, Yong Wang
Summary: The migration of hydrogen atoms from metal particles to a nonreducible oxide support is limited by thermodynamics, but this process can be promoted by small oxygenate molecules, leading to improved hydrodeoxygenation rates. This finding offers a molecule-assisted approach to the design and optimization of multifunctional heterogeneous catalysts on non-reducible oxides.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Tanmayi Bathena, Truc Phung, Scott R. Svadlenak, Yu Liu, Lars C. Grabow, Konstantinos A. Goulas
Summary: In this study, PdxCuy/SiO2 and PdxAgy/SiO2 catalysts were investigated for oxygenate upgrading in biofuels. The selectivity was found to be mainly influenced by geometric effects, while the reaction rate of the catalysts was dominated by the electronic effects of alloying.
Article
Chemistry, Physical
Ari F. Fischer, Enrique Iglesia
Summary: Support effects in alkene and arene hydrogenations on metal catalysts attributed to hydrogen spillover are caused by the desorption and hydrogenation of Pt-bound intermediates at acid-base pairs on certain oxides. Toluene-H2 reactions on Pt nanoparticles dispersed on SiO2 occur on surfaces with diverse coverages and reactivity, leading to preferential occupation by less reactive isomers. These less reactive species can desorb as methylcyclohexadiene molecules, which diffuse to nearby oxide surfaces and react, increasing the abundance of more reactive intermediates at Pt surfaces.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Andrew Hwang, Jason Wu, Andrew Bean Getsoian, Enrique Iglesia
Summary: Reduction-oxidation cycles in oxides are widely used in various applications and require coupling reactions at the surfaces of oxide crystals. CeO2-ZrO2 solid solutions (CZO) were used to study the kinetic relevance of surface reactions and diffusion in O-atom addition and removal. The experiments showed that O-removal rates depend on reductant pressures, while O-addition rates are similar for different reactants and can be affected by the presence of Pt nanoparticles.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Enrique Iglesia, Haefa Mansour
Summary: Kinetic and isotopic measurements, along with theoretical assessments, were used to determine the identity and relevance of elementary steps and bound species in H-2-O-2 reactions on Pt surfaces. The reactions involve two kinetically-relevant O2 dissociation routes, one forming two bound O atoms on Pt atom ensembles within H* adlayers, and the other involving reactions with a H*-H* pair to form weakly bound hydrogen peroxide (*HOOH*). The results provide insights into the reaction mechanisms and can help improve catalytic processes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Nicholas R. Jaegers, Enrique Iglesia
Summary: Ni-based solids are effective catalysts for alkene dimerization, and the nature of their active centers and the identity and relevance of bound species and elementary reactions have been explored. A study shows that Ni centers grafted onto ordered MCM-41 mesopores lead to stable monomers that act as Lewis acid-base pairs and stabilize C-C coupling transition states. Density functional theory (DFT) treatments confirm the involvement of these active centers and pathways, which were not previously considered. The DFT-derived activation barriers for ethene dimerization are consistent with experimental measurements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Yuying Song, Scott Svadlenak, Tanmayi Bathena, Melanie J. Hazlett, William S. Epling, Konstantinos A. Goulas, Lars C. Grabow
Summary: Designing robust catalysts for low-temperature oxidation is crucial for the development of advanced combustion engines. Through computational screening, a PdCu alloy catalyst was discovered that can completely oxidize CO below 150 degrees C without inhibition by NO, propylene, or water. This catalyst can be used together with a PtPd catalyst in a two-bed system to achieve sequential, inhibition-free complete oxidation of CO and 50% NO conversion below 120 degrees C.
Article
Engineering, Environmental
Jinshu Tian, Jian Guan, Mingliang Xu, Shuya Qian, Kai Ma, Shaolong Wan, Zhaoxia Zhang, Haifeng Xiong, Shuai Wang, Yong Wang, Jingdong Lin
Summary: In this study, an efficient method for stabilizing hexagonal boron nitride (h-BN) with high specific surface area (SSA) under harsh conditions was proposed. The vacancy defects in h-BN were repaired with metal ions to significantly improve the antioxidant stability of the material. The repaired h-BN maintained a few-layer structure and exhibited high SSA and strong oxidation resistance, making it an excellent platform for fundamental studies and applications.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Engineering, Chemical
Gengrui Zhang, Yan Li, Yong Chen, Xinning Hao, Xianhua Zhang, Shuai Wang, Jingdong Lin, Yong Wang, Shaolong Wan
Summary: The study designs and prepares a nickel-based syngas methanation catalyst with superior thermal stability, using a special ZnAl2O4 spinel support. The catalyst shows excellent reactivity and stability. The work elucidates the critical role and intrinsic mechanism of the spinel support for the construction of the desired methanation catalysts.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
Yixin Lian, Xin Huang, Dongyu Liu, Lihua Yu, Renke Yu, Weijie Wang, Wang Shuai
Summary: An appropriate addition of Fe2O3 significantly improved the performance of V-Cr-based catalysts in the o-xylene ammoxidation reaction, resulting in increased conversion and yield of the target product. The addition of Fe2O3 altered the physical and acid-base properties of the catalyst, as well as adjusted the ratio of V+4 to V+5 in the active oxide V=O, which promoted the oxidation-reduction process and enhanced the catalyst performance.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Physical
Stephen Kristy, Scott Svadlenak, Adam S. Hoffman, Simon R. Bare, Konstantinos A. Goulas
Summary: This study reports the effects of alloying Cu into silica supported Pd nanoparticles on the catalytic activity, surface composition, and particle structure during CO oxidation. By alloying Cu into Pd nanoparticles, the inhibition of CO oxidation by NO is suppressed without any loss of CO oxidation activity.
APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY
(2024)
Article
Chemistry, Multidisciplinary
Lina Zhang, Qianqian Bao, Bangjie Zhang, Yuanbao Zhang, Shaolong Wan, Shuai Wang, Jingdong Lin, Haifeng Xiong, Donghai Mei, Yong Wang
Summary: The single-atom Pt-1/CeO2 catalyst exhibits remarkable activity for room-temperature formaldehyde oxidation, with the active OlatticeH site on CeO2 near Pt2+ playing a key role. This study provides important insights for the design and synthesis of Pt catalysts for room-temperature HCHO oxidation.
Article
Chemistry, Physical
Yifan Sun, Ye Lv, Wei Li, Jinli Zhang, Yan Fu
Summary: In this study, PtRu electrocatalysts were fabricated on carbon paper via cyclic electrodeposition for the electrocatalytic hydrogenation (ECH) of phenol. The Pt3Ru3 catalyst exhibited excellent activity and stability for the conversion of phenol to cyclohexanol at ambient temperature and various current densities. The in situ Raman spectroscopy and kinetic study revealed the hydrogenation mechanism of phenol over Pt3Ru3 in acidic electrolyte, providing an effective electrochemical strategy for the facile construction of durable electrode materials and efficient phenol hydrogenation.
JOURNAL OF CATALYSIS
(2024)
Article
Chemistry, Physical
Amir Shahzad, Khezina Rafiq, Muhammad Zeeshan Abid, Naseem Ahmad Khan, Syed Shoaib Ahmad Shah, Raed H. Althomali, Abdul Rauf, Ejaz Hussain
Summary: Photocatalytic hydrogen production through water splitting is an effective method for meeting future energy demands. In this study, researchers synthesized a 1 % Ag2S/Cu2S co-doped CdZnS catalyst and found that it can produce hydrogen at a higher rate. The co-doping of Ag2S and Cu2S in the CdZnS catalyst showed a synergistic effect, with Ag2S promoting oxidation reactions and Cu2S promoting reduction reactions.
JOURNAL OF CATALYSIS
(2024)