科创中国

Ionic liquids (ILs) have been widely applied for CO2 separation owing to their distinctive properties, such as nonvolatility, tunability of structures, and good affinity with CO₂. IL-based membranes exhibit hybrid properties of both ILs and membranes, which is a prospective method to achieve efficient CO₂ separation from other light gases. This chapter principally reviewed the research progresses of IL-based membranes for CO₂ separation, including supported IL membranes, poly(ionic liquid) membranes, and IL-based polymer membranes. The CO₂ permeability and selectivity of membrane, the influences of IL structures on membrane separation performance and CO₂ separation mechanism were emphatically analyzed and concluded. The challenges and prospective of IL-based membranes for CO₂ separation are presented.

Lu Bai;Shaojuan Zeng;Jiuli Han;Bingbing Yang;Liyuan Deng;Hongshuai Gao;Xiaochun Zhang;Xiangping Zhang;锁江 张

2018-1-1

Covalent organic frameworks (COFs) are generally obtained as insoluble, cross-linked powders or films, hindering their superior processable properties especially for device implementation. Here, a soluble COF is created with atomically well-organized positive charged centers constrained in the planar direction, exhibiting exceptional solubility through an in situ charge exfoliation pathway. Once dissolved, the obtained true solution retains homogeneity even after standing over a year. Moreover, the as-designed soluble COF contains ordered N-coordinated Fe single atom centers and conjugated structures, providing a small work function (4.84 eV) and superior catalytic performance for oxygen reduction (high half-wave potential of a900 mV). The obtained COF true solution can be directly used as a highly efficient Pt-replaced catalyst for zinc-air flow batteries, generating prominent performance and outstanding stability.

Peng Peng;Lei Shi;Feng Huo;锁江 张;Chunxia Mi;Yuanhui Cheng;中华 向

ACS Nano

2019-1-22

Energetic copper(II) complexes based on 3,5-dinitrobenzoic acid (HDNBA) and 1,5-diaminotetrazole (DAT), Cu(DNBA)₂(H₂O)₂ (1) and Cu(DAT)₂(DNBA)₂ (2) were synthesized and characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. In both complexes, Cu^II was coordinated to a plane tetragon, by four oxygen atoms from two DNBA^– ions and two coordinated H₂O molecules for 1, and by two oxygen atoms and two nitrogen atoms from different DNBA^– ions and DAT ligands for 2. Differential scanning calorimetry (DSC) and thermogravimetry (TG) analyses were employed to measure the thermal decomposition processes and non-isothermal kinetics parameters of the complexes. The thermal decomposition onset temperatures of 1 and 2 are 321 and 177 °C. The apparent activation energies of the first exothermic decomposition peaks of 1 and 2 are 247.2 and 185.2 kJ·mol^–1. Both 1 (35 J, > 360 N) and 2 (12.5 J, > 360 N) are less sensitive than RDX. The catalytic effects on the decomposition of ammonium perchlorate (AP) of 1 and 2 were studied by DSC. All results supported the potential applications of the energetic complexes as additives of solid rocket propellants.

Zhimin Li;Yutao Yuan;Yanqiang Zhang;Long Liu;锁江 张

Zeitschrift fur Anorganische und Allgemeine Chemie

2017

Understanding of energy transport across the solid-liquid interface is essential for the rational design of efficient heat dissipation capabilities. In this work, we show that the molecular orientation of liquid near the solid surface dominates the thermal transport across the imidazolium ionic liquids (IL)/graphene interface via molecular dynamics simulations. The molecular orientation is defined as the parallelism between the imidazole ring in IL and graphene and is controlled by wettability of graphene. Interfacial thermal resistance (ITR) will decrease linearly with the parallelism, which is suitable for IL with different tail chain length (2, 4, 6, and 8). From the linear relationship, a lower limit of ITR for the IL-graphene interface can be predicted, which is on the order of ∼6 m² K/GW and stands for the lower bound of ITR across the solid-liquid interface. Furthermore, it is indicated that the parallel imidazole ring in IL facilitates the thermal transport via shifting the dominating vibrational modes to a higher frequency (∼15 THz). These findings show that the molecular orientation can be an effective factor to control the interfacial thermal transport, which can shed light on the future rational designs of some key chemical engineering processes, such as IL-based coolants, batteries, nanoelectrical devices, and so on.

Cheng Qian;Yanlei Wang;Hongyan He;Feng Huo;Ning Wei;锁江 张

Journal of Physical Chemistry C

2018-9-27

It is critically important to understand the structural properties of ionic liquids. In this work, the structures of cations, anions, and cation-anion ion-pairs of 1,3-dialkylimidazolium based ionic liquids were optimized systematically at the B3LYP/6-31+G* level of DFT theory, and their most stable geometries were obtained. It was found that there exist only one-hydrogen-bonded ion-pairs in single-atomic anion ionic liquids such as [emim]Cl and [emim]Br, while one- and two-hydrogen-bonded ion-pairs in multiple atomic anion ionic liquids such as [emim]BF₄ and [emim][PF ₆ exist. Further studies showed that the cations and anions connect each other to form a hydrogen-bonded network in 1,3-dialkylimidazolium halides, which has been proven by experimental measurement. Furthermore, the correlation of melting points and the, interaction energies was discussed for both the single atomic anion and multiple atomic anion ionic liquids.

Kun Dong;锁江 张;Daxi Wang;Xiaoqian Yao

Journal of Physical Chemistry A

2006-8-10

In allusion to traditional transition-metal oxide (TMO) anodes for lithium-ion batteries, which face severe volume variation and poor conductivity, herein a bimetal oxide dual-composite strategy based on two-dimensional (2D)-mosaic three-dimensional (3D)-gradient design is proposed. Inspired by natural mosaic dominance phenomena, Zn_1-xCo_xO/ZnCo₂O₄ 2D-mosaic-hybrid mesoporous ultrathin nanosheets serve as building blocks to assemble into a 3D Zn-Co hierarchical framework. Moreover, a series of derivative frameworks with high evolution are controllably synthesized, based on which a facile one-pot synthesis process can be developed. From a component-composite perspective, both Zn_1-xCo_xO and ZnCo₂O₄ provide superior conductivity due to bimetal doping effect, which is verified by density functional theory calculations. From a structure-composite perspective, 2D-mosaic-hybrid mode gives rise to ladder-type buffering and electrochemical synergistic effect, thus realizing mutual stabilization and activation between the mosaic pair, especially for Zn_1-xCo_xO with higher capacity yet higher expansion. Moreover, the inside-out Zn-Co concentration gradient in 3D framework and rich oxygen vacancies further greatly enhance Li storage capability and stability. As a result, a high reversible capacity (1010 mA h g^-1) and areal capacity (1.48 mA h cm^-2) are attained, while ultrastable cyclability is obtained during high-rate and long-term cycles, rending great potential of our 2D-mosaic 3D-gradient design together with facile synthesis.

Jia Yu;Yanlei Wang;Lihui Mou;Daliang Fang;Shimou Chen;锁江 张

ACS Nano

2018-2-27

In this work, we studied the effects of salts on the self-assembly of two-dimensional graphene oxide (GO) driven by the dissolution of a sub-microliter droplet. Two kinds of structures were obtained. One was a GO snowball with small salt crystals inserted between sheets, which formed with a low initial concentration of insoluble salt in the GO dispersion. The other was a hybrid nanostructure containing NaCl or KCl crystals on a GO snowball, which formed with a high initial salt concentration in the suspension. In addition, we report the novel nanodent-decorated GO snowballs formed by templating the spontaneously formed microdroplets through ouzo effects. Such highly crumpled snowball structures may find applications in super-capacitors or catalyst supports.

Yuting Song;Haijun Yang;Yufei Wang;Shimou Chen;Dan Li;锁江 张;Xuehua Zhang

Nanoscale

2013-7-21

Four energetic salts (including two ionic liquids) based on 2-(dimethylamino)-N,N,N-trimethylethanaminium and N,N′-dialkyl-N,N,N′,N′-tetramethylethane-1,2-diaminium was prepared and characterized by ¹H- and ¹³C-NMR, infrared and Raman spectroscopies, and elemental analysis. Their physicochemical properties such as melting and decomposition temperatures, density, viscosity, heat of formation, detonation performance, and specific impulse were measured or calculated. With thermal stability up to 200°C, the resulting ionic liquids show densities from 1.02 to 1.19 g cm⁻³ and heats of formation from 85.1 to 154.4 kJ mol⁻¹. Moreover, 2-(dimethylamino)-N,N,N-trimethylethanaminium dicyanamide is hypergolic with the oxidizer (100% HNO₃) and exhibits potential as a green fuel for bipropellants.

Teng Fei;Huiwu Cai;Yanqiang Zhang;Long Liu;锁江 张

Journal of Energetic Materials

2016-4-2

In this paper the extended Debye-Huckel formula is used to represent the activity coefficient of solvated ions, and osmotic coefficient φ in the formula is cancelled by mathematical treatment. So a new formula for electrolytic activity coefficient, which contains only a single parameter h, is established. In order to test the reliability and practicability of the new formula, the activity coefficients of 48 electolyte-containing systems reported in literature are calculated. The results show good accuracy. Generally, the mean relative deviation of every processed system is less than 0.8%.

锁江 张;Shijun Han

Huagong Xuebao/CIESC Journal

1994-6

A series of thermally stable pyridinium-based ionic liquids (ILs), including [C₄Py][BF₄], [C₆Py][BF₄], [C₈Py][BF₄], [C₄³MPy][BF₄], [C₆³MPy][BF₄], [C₈³MPy][BF₄], [C₄Py][SCN] and [C₄Py][Tf₂N], were firstly applied as new absorbents for SO₂ capture. It was found that among the investigated ILs [C₄Py][SCN] has the highest absorption capacity of 0.841 gSO₂gIL^-1 under ambient conditions, which is much higher than that of the most reported imidazolium-based ILs. The selectivity for SO₂/CO₂, SO₂/N₂ and SO₂/O₂ was also studied and the higher selectivity for SO₂ to other gases using the [C₄Py][SCN] was achieved. Moreover, how the water content affects the absorption capacity of SO₂ was further investigated. The absorption mechanism was studied using FT-IR and NMR spectroscopy, as well as Quantum Chemical calculation and Molecular Dynamic (MD) simulation. It was demonstrated that the physical absorption occurs in pyridinium-based ILs for SO₂ capture. Comparing with cation of IL, anion plays a dominant role in SO₂ absorption, which was proved both by the interaction enthalpy of IL-SO₂ using Quantum Chemical calculation and the experimental results. MD simulation results further confirmed that the higher absorption capacity of SO₂ in [C₄Py][SCN] is mostly attributed to the stronger electrostatic interaction between the anion and SO₂. In addition, the [C₄Py][SCN] can still keep the stable absorption performance after five cycles of absorption and desorption, implying the pyridinium-based ILs show great potentials as cost effective and green absorbents for SO₂ capture applications.

Shaojuan Zeng;Hongshuai Gao;Xiaochun Zhang;Haifeng Dong;香平 张;锁江 张

Chemical Engineering Journal

2014-9-1