Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Organic
Qing-Qing Kang, Zi-Ying Wang, Sen-Jie Hu, Chun-Mei Luo, Xue-Er Cai, Yong-Bin Sun, Ting Li, Wen-Ting Wei
Summary: Copper-catalyzed cyclization of alkynes plays a significant role in catalytic chemistry. However, the uncontrolled reactivity of the vinyl-Cu-II intermediate limits the selective cyclization in this transformation. This study presents a practical strategy to control the cyclization and oxidative cleavage of the vinyl-Cu-II intermediate, enabling the switchable construction of quinolin-2-ones and quinoline-2,4-diones from alkyne-tethered alpha-bromocarbonyls using a commercially available copper catalyst under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Engineering, Chemical
Hongju Lin, Fanhui Liao, Yanchang Chu, Mingyu Xie, Lun Pan, Yuanyuan Wang, Lijian Leng, Donghai Xu, Le Yang, Gangfeng Ouyang
Summary: A honeycomb NiCo/C-Na catalyst with a micro-meso-macroporous structure has been fabricated and shown to have significantly higher catalytic activity for the decarboxylation of fatty acids. It also proves to be efficient in upgrading sludge HTL bio-crude, resulting in a biofuel with decreased viscosity and increased density.
CHEMICAL ENGINEERING SCIENCE
(2024)
Article
Chemistry, Multidisciplinary
Wen Liu, Maoping Pu, Jun He, Tinghui Zhang, Shunxi Dong, Xiaohua Liu, Yun-Dong Wu, Xiaoming Feng
Summary: This study presents an efficient enantioselective radical carboazidation and diazidation reaction of α,β-unsaturated ketones and amides catalyzed by chiral N,N'-dioxide/Fe(OTf)(2) complexes, enabling the preparation of chiral compounds from substituted alkenes. Control experiments and mechanistic studies confirmed the radical pathway in the reaction process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Peipei He, Bo Chen, Liang Huang, Xixi Liu, Jingzhong Qin, Zehui Zhang, Wen Dai
Summary: A novel and efficient protocol for the direct synthesis of amides via heterogeneous manganese-oxide-catalyzed successive cleavage and amidation of C-C bonds in alcohols is reported. This method shows high catalytic activity for a wide range of primary and secondary alcohols, as well as model compounds, resulting in the formation of shorter-chain amides.
Article
Chemistry, Organic
Swagata Baruah, Sabera Sultana, Pratiksha Bhorali, Pallabi Saikia, Sanjib Gogoi
Summary: A novel Ru(ii)-catalyzed decarbonylative annulation and direct C-H functionalization reaction of phthalic anhydrides with acrylates is reported, providing an efficient route for the synthesis of 3,7-disubstituted phthalides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Guangying Tan, Mowpriya Das, Ivan Maisuls, Cristian A. Strassert, Frank Glorius
Summary: The rhodium-catalyzed dealkenylative arylation of alkenes with arylboronic compounds provides an unconventional access to bi(hetero)aryls with excellent chemoselectivity. This method enables the cleavage of C(aryl)-C(alkenyl) and C(alkenyl)-C(alkenyl) bonds in various alkenes and 1,3-dienes, leading to the efficient construction of novel organic fluorescent molecules with excellent photophysical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xin-Lian Liu, You-Ya Zhang, Lin Li, Lu-Qi Tan, Yin-Ai Huang, Ai-Jun Ma, Jin-Bao Peng
Summary: In this study, a palladium-catalyzed ligand-controlled selective addition and cycloaddition reaction was developed for the preparation of organic compounds.
Article
Chemistry, Organic
Rodney A. Fernandes, Praveen Kumar, Amit Bhowmik, Dnyaneshwar A. Gorve
Summary: This research reveals a straightforward, effective, and environmentally friendly photocatalytic method for the regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes. The method features mild reaction conditions, ambient temperature, excellent regioselectivity, and compatibility with a wide range of functional groups.
Article
Chemistry, Multidisciplinary
Huan Zhang, Enhui Wang, Shasha Geng, Zhengli Liu, Yun He, Qian Peng, Zhang Feng
Summary: The iron-catalyzed defluorosilylation reaction is an efficient, highly functional-group compatible, and stereo- and regioselective reaction that can be used for late-stage silylation of biologically relevant compounds, offering opportunities for applications in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Lei-Yang Zhang, Nai-Xing Wang, Yue-Hua Wu, Zhan Yan, Xue-Wang Gao, Ke Feng, Bao-Cai Xu, Yalan Xing, Pei-Jia Wang, Yao Zhang, Le-Le Gao
Summary: The synthesis of bioactive amides was achieved by generating secondary amides with an aldehyde group through the reaction of aldehydes and secondary amines. Various (hetero)aryl aldehydes and aliphatic aldehydes were successfully converted into the desired products in moderate to excellent yields. A plausible mechanism involving a Cu(I/II/III) catalytic cycle combined with radical rearrangement was proposed and confirmed with the detection of four key intermediates by high-resolution mass spectrometry.
Article
Chemistry, Organic
Young Woo Kang, Ran Hui Kim, Shafrizal Rasyid Atriardi, Sang Kook Woo
Summary: We developed a photocatalyzed Giese reaction method that overcomes the substrate scope limitations and shows good functional groups tolerance, achieving high yields. The reaction mechanism involves in situ generation of an alkoxymethyl radical via single-electron oxidation of alpha-trimethylsilyl-substituted ethers.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jian-Xing Xu, Zhi-Peng Bao, Xiao-Feng Wu
Summary: The transformation of carbon monoxide and ethylene into high value-added chemicals, particularly multifunctionalized compounds, is economically significant. A palladium-catalyzed thiocarbonylative 1,2-difunctionalization of ethylene was developed, resulting in successful conversion of organic disulfides into beta-thiopropionate thioesters with good yields.
Article
Chemistry, Multidisciplinary
Yao Ge, Fei Ye, Ji Yang, Anke Spannenberg, Haijun Jiao, Ralf Jackstell, Matthias Beller
Summary: A novel palladium-catalyzed cascade carbonylation is described for the direct and selective synthesis of alpha,beta-unsaturated piperidones, generating a broad range of intriguing heterocycles from easily available propargylic alcohols and aliphatic amines. The success of this transformation hinges on the catalytic cleavage of the carbon-carbon triple bond by a specific catalyst with 2-diphenylphosphinopyridine as ligand and suitable reaction conditions, with mechanistic studies pointing to the importance of branched unsaturated acid 11 as a crucial intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shihao Xin, Xinxin Peng, Yao Zhang, Aiguo Zheng, Changjiu Xia, Min Lin, Bin Zhu, Zuoxin Huang, Xingtian Shu
Summary: A binary catalyst composed of tungsten oxide (WO3) and spongy titanosilicate (STS) zeolite is proposed for the oxidative cleavage of methyl oleate (MO). The STS component converts MO to desired products, while reducing the formation of unwanted byproducts. Additionally, STS promotes the precipitation of tungsten species, effectively reducing tungsten leaching. The WO3-STS binary catalyst exhibits high conversion and selectivity, and maintains excellent performance over multiple recycling reactions.
Correction
Chemistry, Multidisciplinary
Matteo Monai, Marianna Gambino, Sippakorn Wannakao, Bert M. Weckhuysen
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Rakesh Sen, Shounik Paul, Sriram Krishnamurthy, Anupama Devi, Ethayaraja Mani, R. J. M. Klein Gebbink, Soumyajit Roy
Summary: This study demonstrates with experimental evidence how the emulation of space-time symmetry breaking by electrochemical realization of a Time-Gel' can lead to the creation of matter. Time-Gel' is realized by inducing the gelation phenomenon of discrete molecular precursors, and the temporal information descriptor (Q) exhibits a power-law relationship (Q proportional to Phi(g)^n) with the volume fraction of the gel (Phi(g)). The exponent n is 5, indicating the divergence in matter creation. This finding further supports the understanding that the breaking of symmetry under conditions following Noether's theorem leads to the emergence of matter. In summary, this research proposes the idea of symmetry breaking and presents the electrochemical realization of the Time-Gel' model as an alternative explanation for the creation of matter based on Chemical Science.
JOURNAL OF THE INDIAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Guusje Delen, Matteo Monai, Katarina Stanciakova, Bettina Baumgartner, Florian Meirer, Bert M. Weckhuysen
Summary: Researchers have discovered that the sorption and conversion of gaseous molecules on the surface of functional materials preferentially occur on specific undercoordinated high-index surface sites. By combining in situ PiFM with DFT calculations, they have studied the site-specific sorption and conversion of formaldehyde on faceted ZIF-8 microcrystals and observed preferential adsorption on high-index planes. They have also visualized unsaturated nanodomains and found structure sensitive conversion mediated by Lewis acidity on defective ZIF-8 crystals.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Physical
Javier Perez-Ramirez, Bert M. Weckhuysen, Maria E. Southall
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Laurens D. B. Mandemaker, Christia Jabbour, Nikolaos Nikolopoulos, Joren M. Dorresteijn, Miguel Rivera-Torrente, Bert M. Weckhuysen
Summary: The growth mechanisms and molecular phenomena of UiO-67, UU-1, and ZIF-8 metal-organic framework (MOF) films on transparent substrates are studied using transmission-based characterization. UiO-67 follows a Volmer-Weber growth mechanism with assistance from solution-grown seeds. UU-1 exhibits fiber-like morphology and inter-fiber macroporosity, while ZIF-8 shows a similar Volmer-Weber growth mode. CO probe molecule adsorption FT-IR spectroscopy reveals the effects of methanol exposure, with UiO-67 becoming inaccessible to CO, UU-1 undergoing a topotactic transformation, and ZIF-8 remaining stable with impurity removal. This approach opens new possibilities for studying other film materials using transmission-based spectroscopy.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Green & Sustainable Science & Technology
Agneev Mukherjee, Pieter Bruijnincx, Martin Junginger
Summary: The maritime sector accounts for a significant amount of global greenhouse gas emissions and is facing pressure to decarbonise. Renewable fuels show potential, but their high costs are a barrier. Carbon Capture and Storage (CCS) can enhance marine fuel decarbonisation, but adds to the cost. This study compares the costs of four renewable carbon fuels and considers the impact of carbon taxation. The results show that without carbon taxation, renewable fuels are not competitive, and methanol and DME produced using CO2 capture are the most cost-effective options.
RENEWABLE & SUSTAINABLE ENERGY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Arjan T. Smit, Emanuela Bellinetto, Thomas Dezaire, Oussama Boumezgane, Luke A. Riddell, Stefano Turri, Michiel Hoek, Pieter C. A. Bruijnincx, Gianmarco Griffini
Summary: This study presents a novel strategy for tailoring lignin molar mass and hydroxyl group reactivity in polyurethane (PU) coatings. By fractionation and partial depolymerization, lignin fractions with specific molar mass ranges were obtained, allowing the production of coatings with different properties. The study also shows that lignin depolymerization can significantly improve lignin reactivity and enhance coating flexibility.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Arjan T. Smit, Thomas Dezaire, Luke A. Riddell, Pieter C. A. Bruijnincx
Summary: Lignin partial depolymerization by reduction (PDR) is a strategy to modify the molar mass and heterogeneity of technical lignin, and increase its reactivity in polymer applications. The process aims to break the remaining lignin beta-O-4 linkages, reducing the molar mass of large lignin fragments. The PDR process provides control over key lignin characteristics, allowing for tailored biobased polymer properties.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Thuy T. Le, Wei Qin, Ankur Agarwal, Nikolaos Nikolopoulos, Donglong Fu, Matthew D. Patton, Conan Weiland, Simon R. Bare, Jeremy C. Palmer, Bert M. Weckhuysen, Jeffrey D. Rimer
Summary: This study reveals that the presence of a catalytically inactive siliceous exterior rim on ZSM-5 particles can significantly reduce diffusion limitations, leading to an improved catalyst lifetime. The synthesis of Si-zoned ZSM-5 catalysts improves the diffusion properties of the catalyst. Operando ultraviolet-visible light diffuse reflectance spectroscopy shows a substantial reduction in external coking among Si-zoned samples. Molecular dynamics simulations demonstrate that there are significantly reduced transport limitations in the zoned regions, which contributes to the improved catalyst activity of Si-zoned zeolites compared to ZSM-5 with a homogeneous acid-site distribution.
Article
Chemistry, Multidisciplinary
J. J. Erik Maris, Luke A. Parker, Katarina Stanciakova, Nikolaos Nikolopoulos, Koen M. H. Berendsen, Alfons van Blaaderen, Florian Meirer, Freddy T. Rabouw, Bert M. Weckhuysen
Summary: In this study, we used confocal laser scanning microscopy to investigate the molecular accessibility and diffusion of a small fluorescent dye molecule, resorufin, in the hierarchical, anisotropic pore structure of large zeolite-beta crystals. Our findings revealed that protonated resorufin exhibits strong fluorescence when confined within zeolite micropores, enabling fluorescence microimaging experiments. Through our experiments, we were able to characterize the pore space and quantify the diffusion coefficient in the straight pores of zeolite-beta. We also observed that diffusion is impeded when crossing the boundaries between zeolite subunits.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Florian Zand, Suzanne J. T. Hangx, Christopher J. Spiers, Peter J. van den Brink, James Burns, Matthew G. Boebinger, Jonathan D. Poplawsky, Matteo Monai, Bert M. Weckhuysen
Summary: Understanding and controlling the structure and composition of nanoparticles in supported metal catalysts are crucial for improving chemical processes. Atom probe tomography (APT) is a powerful tool for three-dimensional chemical imaging of materials with nanometer resolution. However, APT has not been used for mesoporous oxide-supported metal catalysts due to sample fracture. In this study, we developed a high-pressure resin impregnation strategy to overcome this issue and successfully applied APT to high-porous supported Pd-Ni catalyst materials active in CO2 hydrogenation. Our results demonstrate the capability of APT to quantitatively assess the size, composition, and metal distribution of nanoparticles in industrial catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Luke A. Riddell, Floris J. P. A. Enthoven, Jean-Pierre B. Lindner, Florian Meirer, Pieter C. A. Bruijnincx
Summary: In order to fully utilize the potential of kraft lignin in material applications, it is important to have precise control over physicochemical parameters that determine the properties of lignin-derived materials. This study demonstrates that fractionation combined with systematic modification offers a powerful strategy to expand and tailor the properties of lignin. The glass transition temperature (Tg) of kraft lignin can be tuned over a significant range, allowing for precise control over this key property.
Article
Chemistry, Multidisciplinary
Pouya Zaree, Ilhan Tomris, Sander D. de Vos, Roosmarijn van der Woude, Frits M. Flesch, Robertus J. M. Klein Gebbink, Robert P. de Vries, Roland J. Pieters
Summary: A miniaturized sensor containing graphene- and gold nanoparticles was functionalized with proteins for electrochemical detection. The interactions between molecules and proteins were observed and quantified using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The protein binders included carbohydrate ligands as small as carbohydrates and COVID-19 spike protein variants engaged in protein-protein interactions.
Article
Chemistry, Multidisciplinary
Razvan C. Cioc, Eva Harsevoort, Martin Lutz, Pieter C. A. Bruijnincx
Summary: Diels-Alder cycloaddition is an important transformation in chemistry, especially in the synthesis of versatile bio-based platform molecules. However, the reactivity of common furanic compounds presents a major challenge for industrial applications. In this study, we report a highly efficient intramolecular Diels-Alder reaction between allyl acetals of different furfurals, resulting in the formation of oxanorbornene derivatives with high chemo-, regio-, and stereoselectivity. These derivatives can be easily diversified into valuable products, offering potential for scalable production of renewable chemical building blocks from inexpensive bioderived platform molecules.
Article
Chemistry, Multidisciplinary
Mark J. J. Mangnus, Vincent R. M. Benning, Bettina Baumgartner, P. Tim Prins, Thomas P. van Swieten, Ayla J. H. Dekker, Alfons van Blaaderen, Bert M. Weckhuysen, Andries Meijerink, Freddy T. Rabouw
Summary: This study investigates the influence of solvent and gas environments on the photoluminescence (PL) properties of lanthanide-doped nanocrystals, and explains the changes in PL spectrum and excited-state lifetimes using energy transfer mediated by molecular vibrations. EVET-mediated quenching holds promise for probing the local chemical environment of nanocrystals dispersed in a liquid or exposed to gaseous molecules.
Article
Chemistry, Physical
Zi-Ye Liu, Qian-Yu Wang, Ji-Ming Hu
Summary: In this study, a layered carbon dot composite catalyst (NiFe LDH@CDs) was prepared using a one-step coprecipitation method, without the need for heating or hydrothermal treatment. The CD-functionalized catalyst facilitated rapid charge transfer and accelerated the oxygen evolution reaction. Additionally, the heterojunction structure formed between NiFe LDH and CDs efficiently suppressed photoelectron-hole recombination.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Rohit Kumar, Ankit Kumar Srivastava, Palaniyappan Nagarasu, Vedichi Madhu, Ekambaram Balaraman
Summary: We designed and synthesized a NN-CoII bidentate complex and used it for the amination of alcohols under mild and solventless conditions. The complex exhibited good reactivity towards both primary and sterically hindered secondary alcohols, providing high yields of amines. The pyrazole moiety in the ligand played a crucial role in the reaction. Furthermore, we demonstrated the reusability of the complex as a homogeneous cobalt catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shivanand Chettri, Liang-Ting Wu, Sagarmani Rasaily, Debesh Sharma, Bikram Gurung, Rajani Dewan, Sudarsan Tamang, Jyh-Chiang Jiang, Anand Pariyar
Summary: Replicating the enzymatic surface microenvironment in vitro is challenging, but constructing an analogous model could facilitate our understanding of surface effects and aid in developing an efficient bioinspired catalytic system. In this study, five unique Cu2O morphologies were generated, and the surface morphology variations were found to be a consequence of differences in the exposure of low-index facets. The reactivity of Cu2O was found to be influenced by the proportion of {110} planes, with r-Cu2O exhibiting the highest reactivity.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Yong Tang, Jianhao Qiu, Dingliang Dai, Guanglu Xia, Lu Zhang, Jianfeng Yao
Summary: Defect engineering has been shown to improve the photocatalytic performance. This study investigated the use of defect-rich UiO-66-NH2 wrapped by ZnIn2S4 as a catalyst for photocatalytic H2O2 production. The defects in UiO-66-NH2 enhanced O-2 adsorption and charge separation, leading to higher H2O2 yield. The insights from this work can advance the research in defect engineering of MOFs and photocatalytic H2O2 synthesis.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Ruiyang Qu, Shuxin Mao, Jana Weiss, Vita A. Kondratenko, Evgenii V. Kondratenko, Stephan Bartling, Haifeng Qi, Annette-Enrica Surkus, Kathrin Junge, Matthias Beller
Summary: The hydrogenation of amides, a challenging reaction usually performed at high temperatures, has been achieved under milder conditions using a new Pt-MoOx/TiO2 catalyst. This catalyst system enables the selective hydrogenation of various amides and imides.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Xiaoran Niu, Ao Wang, Lei Tong, Lei Wang, Yuan Kong, Chenliang Su, Hai-Wei Liang
Summary: This study introduces a novel intermetallic PdCu3 catalyst supported on defective nanodiamond-graphene (ND@G), which exhibits high selectivity (95%) and remarkable activity (turnover frequency: 2940 h(-1)), six times higher than that of the commercial Lindlar catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Review
Chemistry, Physical
Zhiyuan Zheng, Yiming Yue, Hongying Zhuo, Qinggang Liu, Yanqiang Huang
Summary: This review presents the recent research advances on single-atom catalysis for deep reduction of CO2. Detailed introductions and summaries were classified into three categories based on proton-coupled multi-electron transfer approaches: strengthening metal-support interaction, rational design and regulation of coordination environment, and development of SACs with multi-atom active sites. The challenges and future research directions in the field of SACs for CO2 reduction are also proposed.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shiv Kumar, Paramita Datta, Anup Bhunia, Swadhin K. Mandal
Summary: This article reports a transition-metal-free process for in situ denitrogenation of tosylhydrazones, resulting in the production of various sulfones. The authors used a phenalenyl-based odd alternant hydrocarbon as a photoredox catalyst, which acted as a potent oxidant to facilitate the denitrogenation reaction. The method showed wide functional-group tolerance and high yields, making it suitable for late-stage modification of natural products.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
L. A. Luque-Alvarez, J. Gonzalez-Arias, F. Romero-Sarria, T. R. Reina, L. F. Bobadilla, J. A. Odriozola
Summary: Currently, the production of acetic acid through the carbonylation reaction of methanol has limitations, leading to the exploration of alternative methods using heterogeneous catalysts. This study investigates the methanol carbonylation reaction over a Cu-H-MOR catalyst and proposes a reaction mechanism based on the catalytic behavior and performance of the catalyst. The results provide insights into the reaction mechanism and the involvement of acid and redox centers.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)