Article
Materials Science, Multidisciplinary
Liping Lan, Jiajun Ye, Wenxin Ji, Xiong Gao, Lijuan Liu, Yonggang Sun, Yuanyuan Li, Yulong Ma
Summary: In this study, a theoretical investigation was conducted to design an electron-donating ligand, H2bpdc, which was then used to synthesize Rh(I)-H2bpdc catalyst for methanol carbonylation. The catalyst exhibited an asymmetric double-serrate seven-membered ring coordination structure, which resulted in improved catalytic activity by reducing the energy barrier of the rate-determining step. The catalyst performed exceptionally well in terms of yield, selectivity, and stability, making it a promising candidate for industrial applications.
MATERIALS TODAY COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Lorenzo Arnal, Daniel Escudero, Sara Fuertes, Antonio Martin, Violeta Sicilia
Summary: This article describes the reaction mechanism of complexes [{Pt(C<^>C*)(mu-pz)}2] with methyl iodide and benzyl bromide, as well as the structure and spectroscopic properties of the products.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Roberto Sole, Sofia Toldo, Marco Bortoluzzi, Valentina Beghetto
Summary: The unprecedented palladium catalysed carbonylation of benzyl acetate derivatives presented in this study allows for the synthesis of a broad range of alkyl arylacetates in excellent yields. This reaction does not require the use of halogen or base additives, and can be conducted under carbon monoxide ambient pressure, increasing its sustainability. The best performing catalyst was found to be the binary system palladium acetate (2 mol%)/DPPF (4 mol%), which demonstrated successful carbonylative transformations under specific conditions.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Organic
Xiao-Hong Wei, Chun-Yuan Bai, Ai-Jun Wang, Qiao-Liang Feng, Lian-Biao Zhao, Ping Zhang, Zhen-Hua Li, Qiong Su, Yan-Bin Wang
Summary: An efficient method for the Lewis acid promotion of the synthesis of 9-phosphoryl fluorenes has been developed, focusing on ketone phosphonylation to form a C-P bond and a C-C bond between diphenylmethanone and H-phosphinate esters, H-phosphites, and H-phosphine oxides via phospha-aldol elimination. This method allows for the selective formation of a series of 9-phosphoryl fluorene derivatives in moderate to excellent yields.
Article
Chemistry, Applied
Natalia Kolesnichenko, Tatiana I. Batova, Anton N. Stashenko, Tatiana K. Obukhova, Evgeny Khramov, Alexey A. Sadovnikov, Denis E. Zavelev
Summary: This article investigates the catalytic properties of single atom rhodium catalysts based on microporous ZSM-5 zeolite in the reaction of oxidative methane carbonylation to acetic acid. The results suggest that rhodium exists as single atom metal sites in the zeolite structure and the spatial arrangement of rhodium atoms influences the formation of acetic acid.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Joshua D. Tibbetts, Danilo Russo, Alexei A. Lapkin, Steven D. Bull
Summary: An efficient elevated-pressure catalytic oxidative process has been developed for the oxidation of p-cymene into terephthalic acid with a yield of around 70%. The mixed Co2+/Mn2+ catalytic system allows for high yields of terephthalic acid at relatively low reaction temperatures in short reaction times. The use of different catalytic systems can result in the partial oxidation of p-cymene into different products under varying conditions.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Organic
Xinyi Ren, Lin Tang, Chaoren Shen, Huimin Li, Peng Wang, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification-cyclization method was developed for efficient preparation of enantioenriched gamma-lactams, with good selectivities and a broad substrate scope. The correlation between multiple selectivities and N-substitutes of the amide linker in the substrate was demonstrated through crystallographic evidence and control experiments.
Article
Chemistry, Physical
Chen -Wei Wang, Yuan Sun, Li-Jun Wang, Wen-Hua Feng, Yu -Ting Miao, Ming -Ming Yu, Yu-Xuan Wang, Xu-Dong Gao, Qingqing Zhao, Zhiqin Ding, Zhaochi Feng, Si-Min Yu, Jinhui Yang, Yongfeng Hu, Jian-Feng Wu
Summary: Herein, we report a direct co-conversion of methane, carbon monoxide, and hydrogen peroxide into acetic acid, catalyzed by Fe/ZSM-5 (0.25) zeolite under mild conditions, achieving a high acetic acid yield with optimal selectivity. C-13-Tracking experiments revealed the origin of methyl and carbonyl groups in acetic acid. Spin-trapping experiments indicated the involvement of center dot OH and center dot CH3 radicals. In situ Raman analysis suggested a potential intermediate -Fe-OCH3 species. Overall, our method is greener and more economical, showing potential as an industrial alternative.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Review
Chemistry, Physical
Lalit Kumar, Sonal Asthana, Bharat Laxman Newalkar, Kamal Kishore Pant
Summary: This paper provides an overview of the development of the toluene methylation process and proposes a new catalyst design strategy to address the challenges in p-xylene production.
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
(2022)
Article
Chemistry, Physical
Samuel A. Ivko, Alex M. James, Matthew J. Derry, Robert Dawson, Anthony Haynes
Summary: In this study, the methanol carbonylation catalyst was successfully heterogenised within a dispersible microporous polymer support with cationic functionality, allowing stable nanoparticle dispersion to form. The polymer-supported catalyst showed good activity for the carbonylation of MeOH/MeI to give methyl acetate, but activity was found to decrease over longer periods due to leaching of Rh from the support.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Environmental Sciences
Isaac A. Adedara, Oluwatoyin O. Abioye, Gbemisola T. Oyedele, Cynthia N. Ikeji, Blessing A. Afolabi, Joao B. T. Rocha, Ebenezer O. Farombi
Summary: This study evaluated the toxicological impact of PFOA on Nauphoeta cinerea insects. The results showed that PFOA exposure led to reduced locomotory abilities and increased freezing time in the insects, along with changes in several biochemical markers. This indicates that PFOA poses an ecological risk to Nauphoeta cinerea.
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Hong Deng, Minyan Wang, Yong Liang, Xiangyang Chen, Tianhang Wang, Jonathan J. Wong, Yue Zhao, Kendall N. Houk, Zhuangzhi Shi
Summary: Phosphorous-containing heterocycles exhibit markedly different properties than common heterocyclic compounds, but the lack of synthetic methods has made the study of these molecules difficult, especially in terms of constructing P-stereogenic centers. This research presents a simple, versatile method for synthesizing PN-heterocycles with P(V) centers from phosphanamines through palladium catalyzed intramolecular C-P coupling.
Article
Chemistry, Physical
Tian-Hong Jing, Kai-Chun Zhao, Guang-Hui Shi, Yi-Ying Zhuang, Xiao-Chao Chen, Xiao-Li Zhao, Yong Lu, Ye Liu
Summary: A series of bis-P,O-hybrid ligands were synthesized and characterized. The crystal structures showed that the ligand of L2 acted as a typical trans-positioned diphosphine as observed in the complexes Pd(L2)(OAc)2 and Pd(L2)Cl2, but also potentially as a P,P,O-tripodal pincer. Under mild conditions, L2 enabled Pd(OAc)2 to exhibit remarkable performance in the alkoxycarbonylation of vinyl arenes with high activity and excellent regioselectivity.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yaqi Zhao, Lin Zhang, Min Pu, Ming Lei
Summary: The study utilized the density functional theory method to investigate the reaction mechanism of hydrogen activation and ATH of acetophenone catalyzed by a phosphine-free Mn(i)-NNS complex, revealing high catalytic hydrogenation activity and proposing a concerted but asynchronous hydrogen transfer process. The stereoselectivity of ATH catalyzed by the Mn(i)-NNS complex is mainly attributed to noncovalent interactions between the substrate and the catalyst. The theoretical study predicts high stereoselectivity in reactions catalyzed by complexes with H and NCMe ligands, with enantiomeric excess values of 97% and 93%, respectively.
DALTON TRANSACTIONS
(2021)
Article
Materials Science, Paper & Wood
Songlin Wang, Zongjia Song, Hui He, Qian Wang
Summary: Poplar wood sawdust was chemically modified and separated into fractions using a mixture of p-toluene sulfonic acid and formic acid under different conditions. During the process, the rapid and nearly-complete dissolution of wood lignin was achieved by enhancing the cleavage of interunitary bonds. The optimized conditions led to the removal of over 80% of lignin while retaining almost all of the cellulose in the solid residue.
Article
Chemistry, Multidisciplinary
Yanfei Zhang, Liang Qi, Alicia Lund, Peng Lu, Alexis T. Bell
Summary: This study focused on acetone conversion to isobutene over isolated hafnium sites supported on Silicalite-1 and SiO2. It was found that Hf/Silicalite-1 exhibited faster reaction rates due to Hf-OH groups promoting the aldol condensation, while both Hf sites and Si-OH groups contributed to the reaction on Hf/SiO2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Justin C. Bui, Chanyeon Kim, Alex J. King, Oyinkansola Romiluyi, Ahmet Kusoglu, Adam Z. Weber, Alexis T. Bell
Summary: The electrochemical reduction of carbon dioxide (CO2R) driven by renewable electricity offers a promising route for reusing CO2 and producing carbon-containing chemicals and fuels sustainably. Optimizing the catalyst microenvironment and selectivity, as well as controlling the electrolyte and operating conditions, are crucial for achieving economic viability and high product yields.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Correction
Energy & Fuels
Chanyeon Kim, Justin C. Bui, Xiaoyan Luo, Jason K. Cooper, Ahmet Kusoglu, Adam Z. Weber, Alexis T. Bell
Review
Chemistry, Multidisciplinary
Justin C. Bui, Eric W. Lees, Lalit M. Pant, Iryna V. Zenyuk, Alexis T. Bell, Adam Z. Weber
Summary: Electrochemical synthesis using renewable energy to convert feedstocks into chemicals and fuels is promising, but understanding phenomena in porous electrode systems is challenging. Continuum modeling aids in understanding observed behaviors and guiding next-generation device design. Simulating multiscale phenomena in porous electrodes helps understand and improve the performance of electrochemical synthesis devices.
Article
Multidisciplinary Sciences
Hassan A. Aljama, Martin Head-Gordon, Alexis T. Bell
Summary: In this study, a high-throughput screening process using density functional theory was implemented to identify the energetically most favorable active sites in cation exchanged-zeolites, which is important for understanding catalysis and adsorption behaviors in zeolites.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Joseph A. Gauthier, Zhou Lin, Martin Head-Gordon, Alexis T. Bell
Summary: This study investigates the mechanism of CO2RR under experimental conditions and reveals the differences in activation barriers between alkaline and acidic pathways, as well as the kinetic favorability of COH formation under high overpotential.
ACS ENERGY LETTERS
(2022)
Article
Chemistry, Physical
Tianyu Zhang, Justin C. Bui, Zhengyuan Li, Alexis T. Bell, Adam Z. Weber, Jingjie Wu
Summary: In this study, we developed segmented gas-diffusion electrodes (s-GDEs) to improve the management of CO intermediates in tandem catalysts, thereby enhancing C2+ Faradaic efficiency and current density.
Article
Chemistry, Physical
Paul Kim, Jeroen Van der Mynsbrugge, Martin Head-Gordon, Alexis T. Bell
Summary: Passive NOx adsorbers (PNAs) are proposed for trapping NOx in automotive exhaust during cold start. In this study, it is found that Pd+ cations can be formed through water adsorbed on zeolite acid sites and can be fully desorbed by adsorbing NO. These reactions are thermodynamically feasible and Pd+ is not formed in the absence of adsorbed water and can be readily reoxidized to Pd2+ by trace amounts of O2.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Liang Qi, Sonali Das, Yanfei Zhang, Danna Nozik, Bruce C. Gates, Alexis T. Bell
Summary: Catalysts for ethene hydroformylation were prepared by grafting Rh into nests of -SiOZn-OH or -SiOCo-OH species in BEA zeolite. The Rh dispersion increased with increasing M/Rh ratio and had a positive effect on the turnover frequency for ethene hydroformylation. The Co-containing catalyst exhibited higher activity and selectivity than the Zn-containing catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Danna Nozik, Alexis T. Bell
Summary: Ethane and propane derived from shale gas are preferred feedstocks for the production of aromatics. Ga/H-MFI zeolite exhibits high activity and selectivity for light alkane dehydroaromatization, with Ga3+ sites playing a crucial role. The enhanced activity of Ga/H-MFI is attributed to cooperative effects between Ga3+ sites and Bronsted acid protons.
Article
Chemistry, Multidisciplinary
Brooke Soobrian, Alex J. King, Justin C. Bui, Adam Z. Weber, Alexis T. Bell, Frances A. Houle
Summary: Artificial photosynthesis is a promising method to produce commodity chemicals using abundant chemical feedstocks and renewable energy sources. However, affordable and effective hands-on activities for primary school students to demonstrate and teach artificial photosynthesis are lacking. Educating young students on this topic is crucial for developing a diverse next-generation energy workforce. This study confirms that an active learning-based lesson plan using cheap and accessible materials can effectively educate a broad range of young students on artificial photosynthesis, as demonstrated by the improved understanding of fifth grade students before and after the lesson plan.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Nanoscience & Nanotechnology
Alex J. King, Adam Z. Weber, Alexis T. Bell
Summary: A metal-insulator-semiconductor (MIS) structure is an attractive photoelectrode-catalyst architecture for promoting photoelectrochemical reactions, such as the formation of H2 by proton reduction. Understanding how the insulator layer determines the photovoltage and what properties lead to high photovoltages is critical to the development of MIS structures for solar-to-chemical energy conversion.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
John Safipour, Adam Z. Weber, Alexis T. Bell
Summary: Reactive carbon capture (RCC) is a promising solution for carbon capture and utilization. A systematic study found that RCC in aqueous environments is less effective and does not directly reduce into carbamate. Instead, the presence of amine solution suppresses the rate of CO formation while increasing that of H2.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Chanyeon Kim, Alex J. King, Shaul Aloni, Francesca M. Toma, Adam Z. Weber, Alexis T. Bell
Summary: Photoelectrochemical carbon-dioxide reduction (PEC CO2R) is a promising method for producing chemicals and fuels using sunlight, water, and carbon dioxide. However, the focus has been mostly on producing C-1 products, while the production of C2+ products has been rarely demonstrated. In this study, a Cu/TiO2/p-Si photocathode/catalyst structure was investigated to understand the effects of semiconductor-insulator interactions and illumination direction on the performance and product distribution. Coating the Cu surface with a thin bilayer of Sustainion/Nafion significantly enhanced the current density and faradaic efficiency to ethylene.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Annette Bohme, Justin C. Bui, Aidan Q. Fenwick, Rohit Bhide, Cassidy N. Feltenberger, Alexandra J. Welch, Alex J. King, Alexis T. Bell, Adam Z. Weber, Shane Ardo, Harry A. Atwater
Summary: We investigated how the micrometer-scale morphology of a CO2R gas diffusion electrode (GDE) affects the mass transport properties and local CO2R performance. Using fluorescence confocal laser scanning microscopy (CLSM), we created local pOH maps around a copper GDE and observed that pOH decreases in microtrenches compared to the electrode surface. Multiphysics simulations correlated well with experimental measurements and suggested that the decreased pOH inside microcavities leads to enhanced selectivity towards multicarbon products. This study highlights the importance of a GDE's micromorphology on CO2R performance.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)