Article
Chemistry, Multidisciplinary
Lingwu Meng, Xinli Tong, Haijing Sun, Shaoyuan Guo
Summary: This study developed a sustainable and efficient heterogeneous catalytic protocol for the oxidative C-C bond cleavage. Selective conversion of hydrobenzoin to benzaldehyde was achieved using a solid catalyst, which exhibited high catalytic activity due to the generation of active species from oxygen defects. Moreover, the catalyst showed excellent recyclability. The oxidative cleavages of different 1,2-diols were also investigated, achieving good catalytic performance.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Yang Sik Yun, Claudia E. Berdugo-Diaz, David W. Flaherty
Summary: Biomass has received considerable attention as an alternative to petrochemicals in the production of valuable chemicals and fuels. This Perspective discusses significant advancements in understanding the reaction networks and mechanisms, reactive intermediates, and active site motifs for selective production of desired compounds through hydrogenolysis over heterogeneous catalysts. Continuing research into hydrogenolysis reactions faces current challenges and provides opportunities for future exploration.
Article
Chemistry, Physical
Jia-nan Teng, Rui Zhu, Xinglong Li, Yao Fu
Summary: In this study, cobalt oxide hydrate supported on metal oxides was prepared as a catalyst for the oxidative cleavage of C(OH)-C bond in alcohols using molecular oxygen as the oxidant, achieving high selectivity in product formation. The catalyst was characterized using various techniques and a reaction mechanism was proposed based on the results. The heterogeneous catalytic system showed good recycling performance without the need for any additives.
Article
Chemistry, Physical
Chun Gu, Weiqiang Yu, Hanqing Zhao, Song Shi, Penghua Che, Jie Xu, Jin Gao
Summary: Ru/porous silica regulated by templates with different carbon chain lengths exhibit the ability to control the methane yield in biomass polyols hydrogenolysis.
Article
Chemistry, Physical
Xinnan Lu, Roxanne Clement, Yong Lu, Belen Albela, R. Tom Baker, Laurent Bonneviot
Summary: The development of selective and robust heterogeneous oxidation catalysts is crucial for converting biomass-derived platform chemicals. A microwave-assisted synthesis method was used to incorporate vanadium active sites into mesoporous silica, while Al/Ti/Zr/Ce anchoring ions were introduced to minimize vanadium leaching and improve substrate conversion selectivity. The catalysts showed 2D VOx layers stabilized on anchors, with Ti-IV ions proving to be the best for preventing V leaching and Al-III/Zr-IV ions for enhancing substrate conversion selectivity, in the presence of weakly polar solvents like toluene and ethyl acetate as suitable reaction solvents. The high selectivity for C-C bond cleavage suggests a heterogeneous catalytic pathway different from previously reported molecular oxovanadium (V) catalysts.
Article
Chemistry, Physical
Tomohiro Kikuchi, Takeshi Yasui, Yoshihiko Yamamoto
Summary: Transition-metal mediated carbon-carbon single-bond cleavage of cyclopropenes has been achieved via an intramolecular cycloaddition with alkynes, leading to the formation of 1,2-fused cyclopentadienes. Fused cycloheptatrienes were also synthesized through the cycloaddition of cyclopropene-diynes.
Article
Chemistry, Applied
Ilaria Caivano, Selina Bingel, Ivana Cisarova, David Necas, Martin Kotora
Summary: The synthesis of unsymmetrical [7]-helical compounds containing the dispiro[2,1-c]indenofluorene motif has been achieved for the first time, with good yields. The key step in the reaction sequence is the catalytic intramolecular [2 + 2 + 2] cycloaddition of triynediols using various transition metal compounds (Co, Ni, etc.). The resulting cyclotrimerizations are accompanied by dehydro-Diels-Alder reactions, leading to different aromatic compounds depending on the reaction conditions. The enantioselective cyclotrimerization limits were assessed, and the structures of the products were confirmed by single-crystal X-ray diffraction analysis. Additionally, the photophysical properties of selected products were determined.
Article
Chemistry, Multidisciplinary
Jiaoyu Wu, Linqiang Li, Mengtian Liu, Lu Bai, Xinjun Luan
Summary: A novel Pd-0-catalyzed [2+2+1] annulation was proposed for the rapid assembly of tricyclic indoles in a single-step transformation. Experimental results showed that large tert-butyl and benzyl groups were selectively cleaved via an S(N)1 pathway in the presence of smaller alkyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gayathri B. Gange, Amanda L. Humphries, Dmitry E. Royzman, Mark D. Smith, Dmitry Peryshkov
Summary: The metal-free bond activation by carboranyl diphosphine 1-(PBu2)-Bu-t-2-(PPr2)-Pr-i-C2B10H10 involves the formal oxidation of phosphine groups and concomitant reduction of the boron cage in reactions with main group hydrides and alcohols. This new approach is driven by the cooperation between electron-donating exohedral substituents and electron-accepting cluster, and is reminiscent of oxidative addition to transition metal centers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Zhengyi Liu, Shuang Wu, Yiyun Chen
Summary: A selective C(sp(3))-C(sp(3)) cleavage/alkynylation of cycloalkylamides for aminoalkyne synthesis was reported under mild photoredox catalysis. γ- and δ-Aminoalkynes with diverse alkyne and amine substituents were efficiently constructed via amidyl radicals enabled by hypervalent iodine(III) reagents. Catalytic cyclic iodine(III) BI'-OAc facilitated the single-electron oxidation and ring-opening alkynylation of cycloalkylamides.
Article
Chemistry, Physical
Runyou Ye, Maoshuai Zhu, Xufei Yan, Yang Long, Ying Xia, Xiangge Zhou
Summary: This study reveals a chelation-assisted palladium-catalyzed C=C bond cleavage reaction to form alkenyl nitrile, based on a formal group-exchange reaction. The isolated active Pd(II) complex and deuterium-labeled experiment confirm the necessity of the chelation group, proposing a plausible catalytic pathway.
Article
Chemistry, Multidisciplinary
Farnaz Jafarpour, Banafshe Rahimi
Summary: A novel controlled DTBP-mediated oxidative C-S bond cleavage/annulation cascade is developed, allowing benzyl thioethers to form carbonyl intermediates and participate in annulation reactions with alkynes to produce privileged indenone skeletons.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Peng Wu, Yang Gu, Langxing Liao, Yanfei Wu, Jiaoyu Jin, Zhanfeng Wang, Jiahai Zhou, Sason Shaik, Binju Wang
Summary: A coordination switch of the sulfoxide intermediate is involved in the catalysis of non-heme iron EgtB, driven by S/pi electrostatic interactions, which efficiently promotes selective C-S bond formation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Mary Mensah, Richard Tia, Evans Adei, Nora H. de Leeuw
Summary: The potential energy surfaces of the reactions involved in the catalytic cleavage of a model compound of the beta-O-4 linkage in lignin have been studied using different complexes of iridium and cobalt catalysts. Both iridium and cobalt catalysts are active towards the cleavage of the beta-O-4 linkage, with iridium preferring the 'initial C-H addition' pathway and cobalt preferring the 'direct C-O insertion' pathway. The cobalt-catalyzed reaction goes through a two-state reactivity along the preferred pathway.
Article
Chemistry, Multidisciplinary
Yao Wu, Cong Zhao, Yanzhuang Su, Sason Shaik, Wenzhen Lai
Summary: The copper-dependent formylglycine-generating enzyme (FGE) catalyzes the oxygen-dependent oxidation of specific peptidyl-cysteine residues to formylglycine. Our QM/MM calculations provide a likely mechanism for this transformation, suggesting the involvement of a triplet Cu-II-superoxide complex and a Cu-I-alkylperoxo intermediate. The results also indicate that the aldehyde oxygen of the final product originates from O-2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ming-Yi Chen, Ngoc Thanh Thuy Tran, Ahmed Abubakar Alao, Wen-Dung Hsu
Summary: This study demonstrates the significance of surface Pt atom arrangement for the efficiency of ORR in PEMFCs and reveals the correlation between Pt-Pt average distance and O2 dissociation barrier. Furthermore, the study discovers a robust correlation between the level of the catalyst's d-band center and O2 adsorption energy. High-entropy alloy substrates provide potential for controlling Pt arrangement and O2 dissociation barrier.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Eduardo C. Atayde Jr, Babasaheb M. Matsagar, Yu-Cheng Wang, Kevin C. -W. Wu
Summary: This study presents the first application of an acidic MOF, Sulfated MOF-808, in catalyzing the HAA reactions of furan oligomers for the production of biofuel precursors. The catalyst showed high yield, selectivity, and recyclability, making it versatile for different starting materials.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Maria do Carmo Rangel, Francieli Martins Mayer, Soraia Jesus de Oliveira, Sergio Gustavo Marchetti, Fabricio Luiz Faita, Doris Ruiz, Giovanni Saboia, Mariana Kieling Dagostini, Jonder Morais, Maria do Carmo Martins Alves
Summary: This study developed a new catalyst by investigating the effect of magnesium on the catalytic properties of hematite in ethylbenzene dehydrogenation. The catalyst showed important differences in activity, selectivity, and stability, making it a promising candidate for commercial applications.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Yanjun Li, Qian Wang, Hui Tian, Mingyuan Zhu, Yuanyuan Liu
Summary: A novel strategy using microwave-assisted precipitation was proposed to prepare defective CsH3PMo11VO40 catalyst for the oxidation of methacrolein to methacrylic acid. Microwave treatment accelerates crystallization, increases vanadyl species content, and forms defective Keggin structures, thereby enhancing the oxidation capacity of the catalyst.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Rajeshwari Athavale, Sailee Gardi, Fatima Choudhary, Dayanand Patil, Nandkishor Chandan, Paresh More
Summary: In this study, a novel acidic ionic liquid catalyst was prepared and used for the synthesis of bis-indolyl methane derivatives. The catalyst exhibited short reaction times, easy purification, and reusability.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Masatomo Hattori, Takato Hattori, Masakuni Ozawa
Summary: Cu-added gamma-Al2O3 catalysts were prepared with varying Cu loadings and the effects of copper oxidation states on catalytic activity were investigated. The results showed that the addition of copper increased the catalyst activity, but excessive copper loading decreased catalytic activity. XRD and TEM analysis indicated the formation of a solid solution of copper oxide species on the surface of gamma-Al2O3. XAS and TPR data demonstrated variations in copper oxidation states among the catalysts.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Liwei Fang, Shiyang Niu, Shengsen Wang, Yiqing Lu, Yuanhui Cheng
Summary: In this study, PtNi alloy on nitrogen-doped carbon and SnO2 dual-support was designed to modulate the metal-support interaction, resulting in improved catalytic activity and stability for oxygen reduction reaction. The SnO2/PtNi/NC catalyst exhibited a strongly coupled interface, enhanced electron transfer, and higher half-wave potential compared to PtNi/NC and commercial Pt/C.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Shohei Harada, Duanxing Li, Kenta Iyoki, Masaru Ogura
Summary: This study investigates the catalytic performance of a composite catalyst composed of ZnZrOX and H-zeolite for the hydrogenation of CO2. The deactivation of the composite catalyst is influenced by ion exchange of Zn2+ and/or coke, with their effects differing based on the zeolite structure. Separating the grains of the composite catalyst can prevent deactivation.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Laura Proano, Christopher W. Jones
Summary: In this study, NiGa alloy particles supported on CeO2, ZrO2, and ZrO2-CeO2 solid solutions were prepared and characterized. The nature of the support was found to have a significant influence on the catalyst's activity and selectivity, with the crystalline structure of ZrO2 having the greatest impact. Pure ZrO2 showed the highest methanol selectivity and CO2 conversion at high Zr:Ce ratios. In equimolar and Ce-rich conditions, basic sites and oxygen vacancies were found to be the key parameters affecting methanol production.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Liyan Zhang, Yinze Yang, Leilei Zhou, Fengyu Zhao, Haiyang Cheng
Summary: 1,6-Hexamethylenediamine was successfully synthesized via the reductive amination of 1,6-hexanediol using a Ru/PRL(x)-Al2O3 catalyst. The highly dispersed and anchored Ru species, formed by 1,10-phenanthroline (PRL), played a crucial role in the catalytic reaction. The formation of new acid-base pairs, electron deficient Ru species, and smaller nanoparticles contributed to the improved catalytic performances of the Ru/PRL-Al2O3 catalyst.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Anita Horvath, Miklos Nemeth, Andrea Beck, Gyorgy Safran, Valeria La Parola, Leonarda Francesca Liotta, Gregor Zerjav, Matevz Roskaric, Albin Pintar
Summary: This study investigates the catalytic and structural changes caused by the addition of 0.25 wt% indium in a 3% Ni/CeO2-Al2O3 catalyst prepared by impregnation method. The results show that the addition of indium can decrease the activity of the catalyst, but it improves its stability and reduces coking.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Ankush Kularkar, Vaibhav Vilas Khedekar, Sachin D. Chaudhari, Mudavath Ravi, Sadhana S. Rayalu, Penumaka Nagababu
Summary: Efficiently addressing the challenges of photocatalytic CO2 reduction to CH3OH is crucial. This study developed Zn-BTC MOF and its composites with CaIn2S4, achieving highly efficient and robust photocatalytic CO2 reduction to CH3OH under ambient conditions, using H2O2 as the hydrogen source. Among the composites, ZMCIS4 demonstrated excellent performance with a CH3OH evolution of 49100 μmol/g.cat and a quantum efficiency of approximately 78.41%. The enhanced performance was attributed to the production of nascent hydrogen atoms (H center dot) through the photo-splitting of H2O2 on the ZMCIS surface.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Dan Liu, Yudong Li, Chengyu Wang, Haiyue Yang, Rong Wang, Shujun Li, Xiaohui Yang
Summary: In this study, a self-supporting three-dimensional porous Co3O4 nanobelt array decorated on nickel foam (P-Co3O4 -NBA@NF) electrode with numerous active sites was successfully constructed for the oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA). The P-Co3O4 -NBA@NF electrode demonstrated high conversion efficiency, selectivity, and Faraday efficiency, as well as remarkable long-term stability. This research provides a promising electrocatalyst for biomass conversion.
APPLIED CATALYSIS A-GENERAL
(2024)
Article
Chemistry, Physical
Yimin Li, Enggah Kurniawan, Fumiya Sato, Takayoshi Hara, Yasuhiro Yamada, Satoshi Sato
Summary: In this study, several silica-alumina catalysts modified with Ag were examined for the dehydration of 1,3-butanediol to 1,3-butadiene. Among them, an amorphous silica-alumina catalyst (SAL-3) modified with Ag showed the highest improvement in catalytic activity and stability when operated in H2 flow. The generation of reversible acid sites was found to be the reason behind the enhanced activity and stability of this Ag/SAL-3 catalyst. The effects of various parameters on the catalytic activity of Ag/SAL-3, such as reaction temperature, contact time, Ag content, and carrier gas, were investigated.
APPLIED CATALYSIS A-GENERAL
(2024)