Article
Chemistry, Physical
Haishuai Cui, Xiaoqing Liao, Yufan Ren, Yang Zhou, Jing Xiao, Renjie Deng, Yang Lv, Huajie Liu, Pingle Liu, Hai Yang
Summary: In this article, a facile strategy is proposed to synthesize oxygen-defect-rich Co3O4@NC porous nanorods. These materials are proven to have FLPs sites. The oxygen-defect-rich Co3O4@NC exhibits high selectivity and catalytic performance towards cinnamaldehyde.
JOURNAL OF CATALYSIS
(2023)
Review
Chemistry, Physical
Glory A. Russell-Parks, Thomas Gennett, Brian G. Trewyn
Summary: The rise in energy demands and environmental issues related to fossil fuels have led to a surge of interest in hydrogen as a green alternative. Hydrogen's high energy density and potential as an energy and economic power-house make it an attractive option. Significant research has been focused on material-based hydrogen storage, particularly liquid organic hydrogen carriers (LOHC) for reversible hydrogen transportation. Frustrated Lewis pair (FLP) catalysis shows promise in addressing challenges associated with LOHC technology. This review assesses recent literature on the utilization of intermolecular FLP main group catalysts for improved hydrogenation/dehydrogenation processes, highlighting potential hydrogen storage applications and knowledge gaps that require further investigations.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Xiangqing Feng, Wei Meng, Haifeng Du
Summary: This review provides an overview of the important progress made in FLP-catalyzed asymmetric reactions over the past 15 years. The design and synthesis of chiral FLPs, as well as their applications in hydrogenation, hydrosilylation, and transfer hydrogenation, are summarized and highlighted.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Engineering, Environmental
Mingwei Ma, Liping Li, Ge Tian, Zhibin Geng, Xin Zhang, Xu Zhao, Guangshe Li
Summary: Holey layered high-entropy oxide spinel nanocrystals with rich frustrated Lewis pairs (FLPs) were synthesized via a temperature-driven topological transition. The FLPs, created by oxygen vacancies (Lewis acid sites) and proximal surface hydroxyls or surface lattice oxygen (Lewis base sites), exhibit superior catalytic activity towards the transfer hydrogenation reaction of biomass-derived carbonyl compounds at mild conditions. The active regions between FLPs provide a strong driving force for dissociating alcohols and activating carbonyl groups of substrates, as confirmed by attenuated total reflectance-infrared spectroscopy (ATR-IR) analysis, enhancing the catalytic activity. This work develops a new type of hydrogenation catalysts and offers a perspective for creating solid FLPs.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Ranita Pal, Manas Ghara, Pratim Kumar Chattaraj
Summary: This article provides a review of the chemistry of frustrated Lewis pair (FLP) in the activation of small molecules, hydrogenation of CO2, and unsaturated organic species. Experimental works and electronic structure theory calculations are used to gain mechanistic insights into the reactivity of FLPs. The findings can guide the design of more efficient FLP catalysts for hydrogen activation.
Article
Chemistry, Physical
Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: The article discusses the catalytic effect and hydrogen storage potential of Frustrated Lewis Pairs (FLPs) in the hydrogenation process, emphasizing the influence of acidity and alkalinity on the activity and reversibility of FLPs. The study found that FLPs composed of strong acids and relatively weak bases exhibit better reversibility and reaction rates in hydrogenation.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Review
Biochemical Research Methods
Gitanjali Sharma, Paul D. Newman, James A. Platts
Summary: This review discusses the power of quantum chemistry, particularly density functional theory (DFT), in unraveling mechanisms in the field of FLP chemistry. It covers various aspects such as hydrogen activation, borylation, silylation, polymerization, formation of heterocycles, reaction with small gaseous molecules, alkenes, terminal alkynes, and the role of DFT in understanding regio-selectivity, steric effects, London dispersion, and covalent interactions in FLPs.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2021)
Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yannan Zhou, Xuegang Luo
Summary: In this study, the characteristics of frustrated Lewis pairs (FLPs) on albite surfaces were analyzed using density functional theory, and the reaction mechanism for H-2 activation by the FLPs was investigated. The results demonstrate that albite is an ideal substrate material with typical FLP characteristics on its (001) and (010) surfaces. The interaction between the HOMO of H-2 and the SOMO of the Lewis base, as well as the electron acceptance properties of the Lewis acid, are the key factors in H-2 activation. This study provides new insights and a reference for the development of novel solid FLP catalysts using ultramicro channel materials.
Article
Chemistry, Multidisciplinary
Yan Liang, Zhong Zhang, Xiaofang Su, Xiao Feng, Songzhu Xing, Wei Liu, Rui Huang, Yiwei Liu
Summary: Precisely controlling the structure and spatial distance between Lewis acid and Lewis base sites in a porous system is essential for constructing efficient solid frustrated Lewis pair (FLP) catalysts. In this study, FLP sites were constructed in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (Lewis acid) and surface-basic POM with abundant oxygen (Lewis base). The resulting FLP catalyst exhibited high hydrogenation activity, with 55 and 2.7 times higher activity compared to defect-free POM-based MOF and defective MOF without POM, respectively. This work offers a new approach for the precise design of multi-site catalysts for specific substrate activation and synergistic catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Felix Wech, Urs Gellrich
Summary: This review discusses the hydrogenation of organic substrates catalyzed by borane-based frustrated Lewis pairs, with a focus on the mechanistic aspects of these catalytic reactions.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Huaxun Luo, Boyu Zhu, Xiaomin Liu, Xiaomin Zhang, Tianxiang Zhao, Xingbang Hu
Summary: Through experimental and computational studies, it was found that moderately bulky bases can activate hydrogen and serve as catalysts for the hydrogenation of CO2 to formate. Typical frustrated Lewis pairs (FLPs), known for their high efficiency in H2 activation, were found to be less efficient than non-frustrated Lewis pairs (n-FLPs) for this reaction. These results are expected to inspire the development of novel Lewis pair catalyzed reactions.
MOLECULAR CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Zhipeng Lu, Minsoo Ju, Yi Wang, Jonathan M. Meinhardt, Jesus I. Martinez Alvarado, Elisia Villemure, Jack A. Terrett, Song Lin
Summary: This study demonstrates the functionalization of C(sp(3))-H bonds using frustrated radical pairs (FRPs) generated from disilazide donors and an N-oxoammonium acceptor. The FRPs cleave unactivated C-H bonds to provide aminoxylated products, and the reaction selectivity towards tertiary, secondary, or primary C-H bonds can be controlled by tuning the structure of the donor. Mechanistic studies confirm the formation and involvement of radical pairs in the target reaction.
Article
Chemistry, Multidisciplinary
Xiaoyue Zhang, Yahui Sun, Shunlong Ju, Jikai Ye, Xuechun Hu, Wei Chen, Long Yao, Guanglin Xia, Fang Fang, Dalin Sun, Xuebin Yu
Summary: This paper demonstrates a concept of solar-driven reversible hydrogen storage of metal hydrides by utilizing the photothermal effect and catalytic role. The photothermal effect of Cu@MXene raises the temperature of the hydrogen storage material, while the hydrogen pump effect of Ti and TiHx species formed on the surface of MXene reduces the operating temperature, achieving efficient hydrogen storage.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Zhongchen Zhao, Tian Xu, Xuebin Yu
Summary: Metal chalcogenide anodes with a layered structure have potential as K-based electrochemical energy storage devices, but the slow K-ion transport kinetics and poor structural stability hinder their development. This study investigates the energy storage behavior and links it to the capacity degradation of layer-structured WSe2. A single-phased WSe2 with pre-intercalated high K content is designed to overcome capacity degradation. Theoretical calculations demonstrate the beneficial effect of K-ions on boosting the electrochemical performance of WSe2. The novel design enables the pre-intercalated WSe2 anode material to exhibit high reversible specific capacity and cycling stability.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Chongyang Yuan, Tian Xu, Miao Guo, Tengfei Zhang, Xuebin Yu
Summary: In this study, phosphorus-doped Co3O4 was synthesized and it was found that the doping improved the catalytic activity for ammonia borane hydrolytic dehydrogenation. Furthermore, combining phosphorus doping with copper doping showed a strong synergistic effect and greatly enhanced the catalytic H2 generation. This research is important for designing more efficient metal-based nanocatalysts for energy conversion reactions.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Engineering, Environmental
Xiaowei Wu, Qiyao Yu, Yunqiu Li, Jianhua Xu, Jian-Guo Zhang
Summary: State-of-the-art ab initio molecular dynamics (AIMD) simulations were conducted to investigate the construction mechanisms of high-energy all- and high-nitrogen materials under extreme conditions. The results demonstrate that there are two stages in the decomposition process, involving competition between various reactions and higher temperature or pressure accelerates the competition. The study also reveals the formation of nitrogen-rich clusters and the engineering solution for sustainable future of nature.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Engineering, Environmental
Tingwei Wang, Shu Bu, Kun Wang, Lu Zhang, Zhenxin Yi, Chao Zhang, Wenli Cao, Shunguan Zhu, Jianguo Zhang
Summary: By utilizing the furazan skeleton and hydrazide group as targets, a ligand with multiple coordination sites was designed and synthesized. Different crystallization methods were used to prepare four kinds of ECPs with different structures, and their properties were evaluated. The results showed the best performance in terms of physical-chemical properties and detonation performance for specific ECPs.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qamar-un-Nisa Tariq, Yu -fan Bi, Saira Manzoor, Maher-un-Nisa Tariq, Wen-Li Cao, Wen-Shuai Dong, Jian-Guo Zhang
Summary: In this study, two nitrogen-rich energetic cocrystals, DD1 and DD2, based on DNP and DAF, were synthesized and thoroughly analyzed. The results demonstrate that these cocrystals can reduce the acidity and improve the oxygen balance of DNP, making them promising candidates for expanding the applications of DNP in the field of energetic materials.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Lu Zhang, Ting-wei Wang, Wen-shuai Dong, Chao Zhang, Zu-jia Lu, Zun-ning Zhou, Jian-guo Zhang
Summary: Eight kinds of energetic coordination polymers (ECPs) with multi-coordination were synthesized by combining the carbonyl group with coordination potential in biuret with transition metal nitrates and perchlorates (Co2+, Ni2+, Cu2+, and Ag+). The structures of these complexes were confirmed by various analysis techniques. One of the solvent-free ECPs (Cu(BIU)2(ClO4)2) exhibited the best performance, while ECPs 7 and 8 (Ag(BIU)ClO4) showed good detonation performance during hot plate and laser ignition tests. This study suggests that improving ligand's oxygen balance and constructing multidentate coordination structures can be effective strategies for enhancing the performance of laser-sensitive ECPs.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Biochemistry & Molecular Biology
Wen-Shuai Dong, Lu Zhang, Wen-Li Cao, Zu-Jia Lu, Qamar-un-Nisa Tariq, Chao Zhang, Xiao-Wei Wu, Zong-You Li, Jian-Guo Zhang
Summary: In this study, a cation, 3,5-diamino-4H-pyrazol-4-one oxime (DAPO), with good thermal stability was proposed for the study of energetic cations. Three salts of DAPO were synthesized and their structures were verified using various analytical techniques. The thermal stability and energy properties of the salts were evaluated. The results showed that the compounds have high density, acceptable detonation performance, good thermal stability, and satisfactory sensitivity. The intermolecular interactions were also studied, revealing that DAPO is a potential cation for the design and synthesis of novel energetic materials.
Article
Materials Science, Multidisciplinary
Hui Wu, Zhennan Xiong, Yiyang Mao, Huihui Zhang, Yingying Hu, Jun Shen, Baofeng Wang, Xuebin Yu
Summary: Developing new types of metal-ion batteries beyond lithium-ions is progressing quickly, but the lack of appropriate electrode materials has hindered their large-scale applications. In this study, a MoS2/MoO2/CC electrode material is developed, which effectively addresses the issues of ion diffusion distance, conductivity, and volume change. The electrode exhibits high reversible capacities, excellent rate capacities, and long-term cycling stability in magnesium-ion and sodium-ion storage.
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Yuqin Huang, Panyu Gao, Tengfei Zhang, Xiang Zhang, Guanglin Xia, Fang Fang, Dalin Sun, Zaiping Guo, Xuebin Yu
Summary: In this work, an ultra-stable electrode-solid electrolyte composite for high-performance all-solid-state lithium-ion batteries (ASSLIBs) is fabricated by uniformly covering each MgH2 nanoparticle with ultrathin Mg(BH4)(2) layers on the surface of graphene. The presence of Mg(BH4)(2) layers enhances the Li ion conductivity of the graphene-supported MgH2 nanoparticles, resulting in uniform stable interfaces with high ionic and electronic conductivity. Additionally, the stable framework of inactive Li2B6 and the structural support of graphene alleviate volume change and facilitate intimate contact, leading to an ultrahigh specific capacity of 800 mAh g(-1) for MgH2 after 350 cycles at 2 A g(-1).
Article
Chemistry, Multidisciplinary
Wen-chuan Cheng, Jia-min Chen, Liu Deng, Hui-sheng Huang, Jian-guo Zhang, Tong -lai Zhang, Zhi-min Li
Summary: With the development of aerospace science and technology, the thermal decomposition behavior of ammonium perchlorate (AP) directly influences the combustion performance of composite solid propellants. In this study, novel metal-organic frameworks (MOFs) were prepared and derived composite catalysts were generated to improve the thermal decomposition behavior of AP, resulting in enhanced combustion performance of composite solid propellants.
ENERGETIC MATERIALS FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Ting-wei Wang, Zu-jia Lu, Zhen-xin Yi, Zhi-ming Xie, Lu Zhang, Bao-long Kuang, Yan Li, Jian-guo Zhang
Summary: This study investigates the influence of ligand on the performance of new coordination primary explosive. A ligand 1H-pyrrole-2-carbohydrazide (PRCA) was designed and two coordination compounds were prepared. The tests show that ECCs-1 has better thermal stability and sensitivity, and exhibits extremely strong detonation ability.
CRYSTAL GROWTH & DESIGN
(2023)
Review
Chemistry, Multidisciplinary
Qamar-un-Nisa Tariq, Maher-un-Nisa Tariq, Wen-Shuai Dong, Saira Manzoor, Faiza Arshad, Jian-Guo Zhang
Summary: Co-crystal formation is a promising method to enhance the physicochemical and energetic performance of CL-20. By forming new chemical compositions through noncovalent interactions, the properties of energetic materials can be modified. This review provides an overview of HNIW/CL-20-based co-crystals, including their synthetic methods, intermolecular interactions, and physicochemical and energetic properties, as well as discussing their applications, existing problems, and future challenges.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Wenli Cao, Yong Hu, Ting-wei Wang, Wen-Shuai Dong, Jian-Guo Zhang
Summary: In order to explore the potential applications of nitrogen-rich heterocycle-based materials, a multifunctional ligand with a coplanar configuration was provided and a series of its corresponding energetic metal salts were prepared and characterized. The crystal structures and properties of these metal salts were analyzed, showing good thermostability and insensitivity to mechanical stimulation. The combustion energy and formation enthalpy of these salts were determined experimentally, and three new formulations exhibited promising color properties for environment-friendly pyrotechnic components.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Chao Zhang, Ting-Wei Wang, Zu-Jia Lu, Zhen-Xin Yi, Bao-Long Kuang, Shu Bu, Zhi-Ming Xie, Yan Li, Kun Wang, Jian-Guo Zhang
Summary: The structure of energetic compounds plays a crucial role in determining their performance. This study investigates the influence of different substituent positions on the performance of primary explosives. Two Ag(I)-based complexes were prepared using structurally isomeric ligands, and their structures were confirmed. Experimental results show that the substituent position affects thermal stability, mechanical sensitivity, and energy output. ECPs-2, with the substituent at position 4, exhibits stronger explosive power and initiating capability.
DALTON TRANSACTIONS
(2023)
