Co-reporter:Mi Zhang, Tao Wei, A-Man Zhang, Shun-Li Li, Feng-Cui Shen, Long-Zhang Dong, Dong-Sheng Li, and Ya-Qian Lan
ACS Omega September 2017? Volume 2(Issue 9) pp:5684-5684
Publication Date(Web):September 11, 2017
DOI:10.1021/acsomega.7b00752
A nanocomposite polyoxomolybdate (PMo12)–polypyrrole (PPy)/reduced graphene oxide (RGO) is fabricated by using a simple one-pot hydrothermal method as an electrode material for lithium-ion batteries. This facile strategy skillfully ensures that individual polyoxometalate (POM) molecules are uniformly immobilized on the RGO surfaces because of the wrapping of polypyrrole (PPy), which avoids the desorption and dissolution of POMs during cycling. The unique architecture endows the PMo12–PPy/RGO with the lithium storage behavior of a hybrid battery–supercapacitor electrode: the nanocomposite with a lithium storage capacity delivers up to 1000 mAh g–1 at 100 mA g–1 after 50 cycles. Moreover, it still demonstrates an outstanding rate capability and a long cycle life (372.4 mAh g–1 at 2 A g–1 after 400 cycles). The reversible capacity of this nanocomposite has surpassed most pristine POMs and POMs-based electrode materials reported to date.Topics: Batteries; Distribution function; Electric properties; Electrochemical analysis; Inorganic chemistry; Materials science; Nanocomposites; Nanoparticles; Nanostructures; Solid state electrochemistry; Spectra;
Co-reporter:Xiao-Min Li, Long-Zhang Dong, Shun-Li Li, Gang Xu, Jiang Liu, Feng-Ming Zhang, Li-Shi Lu, and Ya-Qian Lan
ACS Energy Letters October 13, 2017 Volume 2(Issue 10) pp:2313-2313
Publication Date(Web):September 11, 2017
DOI:10.1021/acsenergylett.7b00560
A water-stable metal–organic framework (MOF)-based composite, H2SO4@MIL-101-SO3H, configured with functionalized sulfonate groups bound to the polymeric backbone and nonvolatile strong acid H2SO4 encapsulated into pores, is demonstrated as a superior proton-conducting material, owing to the resultant multiple proton-transfer pathways. This solid material exhibits a superprotonic conductivity of 1.82 S cm–1 (70 °C, 90% RH) that is comparable to that of other excellent MOF-based proton conductors reported thus far. More importantly, the splendid conductivity (0.92 × 10–2 S cm–1, −40 °C) of the title material achieves an enormous improvement compared with that of all proton-conducting systems demonstrated at subzero temperatures.
Co-reporter:Feng-Ming Zhang, Long-Zhang Dong, Jun-Sheng Qin, Wei Guan, Jiang Liu, Shun-Li Li, Meng Lu, Ya-Qian Lan, Zhong-Min Su, and Hong-Cai Zhou
Journal of the American Chemical Society May 3, 2017 Volume 139(Issue 17) pp:6183-6183
Publication Date(Web):April 7, 2017
DOI:10.1021/jacs.7b01559
Imidazole molecules were frequently incorporated into porous materials to improve their proton conductivity. To investigate how different arrangements of imidazoles in metal–organic frameworks (MOFs) affect the overall proton conduction, we designed and prepared a MOF-based model system. It includes an Fe–MOF as the blank, an imidazole@Fe–MOF (Im@Fe–MOF) with physically adsorbed imidazole, and an imidazole–Fe–MOF (Im–Fe–MOF), which contains chemically coordinated imidazole molecules. The parent Fe–MOF, synthesized from the exchange of carboxylates in the preformed [Fe3(μ3–O)](carboxylate)6 clusters and multitopic carboxylate ligands, serves as a control. The Im@Fe–MOF was prepared by encapsulating free imidazole molecules into the pores of the Fe–MOF, whereas the Im–Fe–MOF was obtained in situ, in which imidazole ligands coordinate to the metal nodes of the framework. Proton-conductivity analyses revealed that the proton conductivity of Im–Fe–MOF was approximately two orders of magnitude greater than those of Fe–MOF and Im@Fe–MOF at room temperature. The high proton conductivity of 1.21 × 10–2 S cm–1 at 60 °C for Im–Fe–MOF ranks among the highest performing MOFs ever reported. The results of the density functional theory calculations suggest that coordinated imidazole molecules in Im–Fe–MOF provide a greater concentration of protons for proton transportation than do coordinated water molecules in Fe–MOF alone. Besides, Im–Fe–MOF exhibits steadier performance than Im@Fe–MOF does after being washed with water. Our investigation using the above ideal crystalline model system demonstrates that compared to disorderly arranged imidazole molecules in pores, the immobilized imidazole molecules by coordination bonds in the framework are more prone to form proton–conduction pathways and thus perform better and steadier in water-mediated proton conduction.
Co-reporter:Yu-Jia Tang, Chun-Hui Liu, Wei Huang, Xiao-Li Wang, Long-Zhang Dong, Shun-Li Li, and Ya-Qian Lan
ACS Applied Materials & Interfaces May 24, 2017 Volume 9(Issue 20) pp:16977-16977
Publication Date(Web):May 5, 2017
DOI:10.1021/acsami.7b01096
The development of highly efficient and low-cost oxygen evolution electrocatalysts is extremely imperative for the new energy technology. Transition metal carbides have been investigated as remarkable hydrogen evolution reaction (HER) electrocatalysts but undesired oxygen evolution reaction (OER) electrocatalysts and need further study. Here, a cobalt–molybdenum-based bimetallic carbide coated by N-doped porous carbon and anchored on N-doped reduced graphene oxide film (Co6Mo6C2/NCRGO) is synthesized by directly carbonizing the Co-doped polyoxometalate/conductive polymer/graphene oxide (Co-PCG) precursors. The precise control of the Co/Mo molar ratio in the Co-PCG precursor is of critical importance to synthesize pure phase bimetallic carbide of Co6Mo6C2. As the highly active and robust OER electrocatalyst, the Co6Mo6C2/NCRGO composite exhibits excellent activity in alkaline solution, affording a low overpotential of 260 mV versus RHE at 10 mA cm–2, a small Tafel slope of 50 mV dec–1, as well as long-term stability. The superior OER performances are strongly associated with the active Co6Mo6C2 particles, polypyrrole (PPy)-derived N-doped porous carbon, and the conductive RGO films. Remarkably, it is the first evidence that the bimetallic carbides were used as the OER catalysts with such high OER activity.Keywords: bimetallic carbide; Co6Mo6C2; oxygen evolution reaction; PCG; polyoxometalate;
Co-reporter:Feng-Cui Shen, Yu Wang, Yu-Jia Tang, Shun-Li Li, Yi-Rong Wang, Long-Zhang Dong, Ya-Fei Li, Yan Xu, and Ya-Qian Lan
ACS Energy Letters June 9, 2017 Volume 2(Issue 6) pp:1327-1327
Publication Date(Web):May 1, 2017
DOI:10.1021/acsenergylett.7b00229
Electrocatalysts with high intrinsic activity for the oxygen evolution reaction (OER) are greatly desired for sustainable oxygen-based electrochemical energy conversion. In this work, the bimetallic oxide composite consisting of CoV2O6 and V2O5 anchoring on nitrogen-doped reduced graphene oxide (CoV2O6–V2O5/NRGO-1) was synthesized directly by carbonization of the polyoxometalates, ethylenediamine, and graphene oxide precursors. CoV2O6–V2O5/NRGO-1 used as an electrocatalyst exhibits an ultralow overpotential of 239 mV vs RHE at the current density of 10 mA cm–2 and excellent stability in 1 M KOH. Surprisingly, it has high intrinsic activity with the turnover frequency of 1.80 s–1 at the overpotential of 300 mV, which is the highest among the electrocatalysts reported to date. Theoretical calculation proves that the outstanding electrocatalytic performance is attributed to synergistic effects, in which CoV2O6 acts as active sites while the hydrogen bond between V2O5 and intermediate HOO* of the OER greatly decreases the composite adsorption energy, thus reducing the overpotential. Most importantly, the results demonstrate for the first time that intermolecular hydrogen bonding plays a key role in improving electrocatalytic properties for the OER, which reveals a new method of designing novel OER electrocatalysts.
Co-reporter:Shun-Li Li;Rong Chen;Kui Li;Zhen-Hui Kang;Jian-Chun Bao;Shuai-Lei Xie;Long-Zhang Dong
ACS Applied Materials & Interfaces June 15, 2016 Volume 8(Issue 23) pp:14535-14541
Publication Date(Web):2017-2-22
DOI:10.1021/acsami.6b02765
Various porous Zn1–xCdxS/CdS heteorostructures were achieved via in situ synthesis method with organic amines as the templates. Because of the larger radius of Cd2+ than that of Zn2+, CdS quantum dots are formed and distributed uniformly in the network of Zn1–xCdxS. The Zn1–xCdxS/CdS heterostructure with small Cd content (10 at%) derived from ethylenediamine shows very high H2-evolution rate of 667.5 μmol/h per 5 mg photocatalyst under visible light (λ ≥ 420 nm) with an apparent quantum efficiency of 50.1% per 5 mg at 420 nm. Moreover, this Zn1–xCdxS/CdS heterostructure photocatalyst also shows an excellent photocatalytic stability over 100 h.Keywords: CdS quantum dots; heterostructure; in situ synthesis; photocatalytic activity; Zn1−xCdxS/CdS;
Co-reporter:Qing Huang;Tao Wei;Mi Zhang;Long-Zhang Dong;A-Man Zhang;Shun-Li Li;Wen-Jing Liu;Jiang Liu
Journal of Materials Chemistry A 2017 vol. 5(Issue 18) pp:8477-8483
Publication Date(Web):2017/05/10
DOI:10.1039/C7TA00900C
A novel polyoxometalate-based metal–organic framework (POMOF), [PMo8VMo4VIO37(OH)3Zn4][TPT]5·2TPT·2H2O (NNU-11, TPT = tris-(4-pyridyl)triazine), was synthesized. Zn-ε-Keggin fragments were directly connected with TPT ligands generating 2D layers and further interdigitated with each other by π–π stacking interactions to pack into a 3D array. The compound exhibited excellent stability in air and different organic solvents and even in different pH (pH 1–11) aqueous solutions. It can be utilized as an anode material for lithium ion batteries (LIBs) due to the combination of the multi-electron redox property of POM units and the functionalization of MOFs. NNU-11 exhibited a highly reversible capacity of 750 mA h g−1 at a current density of 50 mA g−1 after 200 cycles along with excellent cycle stability and rate performance. More importantly, for the first time, we designed and synthesized a POMOF crystalline structure model supported by π–π stacking interactions to demonstrate that intermolecular π–π stacking interactions are beneficial to promote the performance of LIBs.
Co-reporter:Jiang Liu;Tian-Yi Bao;Xi-Ya Yang;Pei-Pei Zhu;Lian-He Wu;Jing-Quan Sha;Lei Zhang;Long-Zhang Dong;Xue-Li Cao
Chemical Communications 2017 vol. 53(Issue 55) pp:7804-7807
Publication Date(Web):2017/07/06
DOI:10.1039/C7CC03673F
Two extremely rare β-cyclodextrin (β-CD) supported metal-organic frameworks (MOFs), CD-MOF-1 and CD-MOF-2, were induced to crystallize for the first time through a template-induced approach. The targeted CD-MOFs were employed to perform controlled drug delivery and cytotoxicity assays that confirmed their favourable biological potential of being used as drug carriers.
Co-reporter:Yuan-Yuan Wang;Mi Zhang;Shun-Li Li;Shu-Ran Zhang;Wei Xie;Jun-Sheng Qin;Zhong-Min Su
Chemical Communications 2017 vol. 53(Issue 37) pp:5204-5207
Publication Date(Web):2017/05/04
DOI:10.1039/C6CC10208E
Two novel isostructural polyoxometalate (POM)-based metal–organic frameworks (MOFs) with diamond topology, NENU-506 and NENU-507, were hydrothermally synthesized. They not only combine the advantages of both POMs and MOFs, but also show excellent chemical and thermal stability. Notably, NENU-507 exhibited a high reversible capacity of 640 mA h g−1 after 100 cycles when applied as an anode material in lithium-ion batteries.
Co-reporter:Wei Xie;Jun-Sheng Qin;Wen-Wen He;Kui-Zhan Shao;Zhong-Min Su;Dong-Ying Du;Shun-Li Li
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 3) pp:547-552
Publication Date(Web):2017/03/14
DOI:10.1039/C6QI00528D
We successfully synthesized a novel anionic luminescent metal–organic framework (MOF) (NENU-524) with a lonsdaleite topology. NENU-524 contains a trigonal prismatic unit {Zn8(btca)6(2-NH2-bdc)3} that can be regarded as a double secondary building unit with an unusual triply bound triangular frustum geometry. The prepared NENU-524 had a permanent porosity and excellent stability in air. NENU-524 was used as a platform to encapsulate yellow-emitting [Ir(ppy)2(bpy)]+ cations in the nanotube channels of the blue-emitting MOF via an ion-exchange process. The [Ir(ppy)2(bpy)]+@NENU-524 MOF ([Ir(ppy)2(bpy)]+ concentration 3.86 wt%) emitted a pure white light with CIE coordinates of (0.300, 0.336) and a high quantum yield of up to 15.2%. The white light-emitting diodes assembled using [Ir(ppy)2(bpy)]+@NENU-524 as a white phosphor emitted a bright white light, suggesting that the composite is a promising material for use in lighting. The assembled white light-emitting diodes continued to emit a bright white light for up to one month. This simple and feasible approach could be used to develop luminescent luminophor@MOFs composites for practical applications.
Co-reporter:Wei Xie;Jun-Sheng Qin;Wen-Wen He;Kui-Zhan Shao;Zhong-Min Su;Dong-Ying Du;Shun-Li Li
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 3) pp:547-552
Publication Date(Web):2017/03/14
DOI:10.1039/C6QI00528D
We successfully synthesized a novel anionic luminescent metal–organic framework (MOF) (NENU-524) with a lonsdaleite topology. NENU-524 contains a trigonal prismatic unit {Zn8(btca)6(2-NH2-bdc)3} that can be regarded as a double secondary building unit with an unusual triply bound triangular frustum geometry. The prepared NENU-524 had a permanent porosity and excellent stability in air. NENU-524 was used as a platform to encapsulate yellow-emitting [Ir(ppy)2(bpy)]+ cations in the nanotube channels of the blue-emitting MOF via an ion-exchange process. The [Ir(ppy)2(bpy)]+@NENU-524 MOF ([Ir(ppy)2(bpy)]+ concentration 3.86 wt%) emitted a pure white light with CIE coordinates of (0.300, 0.336) and a high quantum yield of up to 15.2%. The white light-emitting diodes assembled using [Ir(ppy)2(bpy)]+@NENU-524 as a white phosphor emitted a bright white light, suggesting that the composite is a promising material for use in lighting. The assembled white light-emitting diodes continued to emit a bright white light for up to one month. This simple and feasible approach could be used to develop luminescent luminophor@MOFs composites for practical applications.
Co-reporter:Xiu Tang;Jia-Hui Zhao;Yu-Han Li;Zi-Ji Zhou;Kui Li;Fu-Tian Liu
Dalton Transactions 2017 vol. 46(Issue 32) pp:10553-10557
Publication Date(Web):2017/08/14
DOI:10.1039/C7DT01970J
Nanoporous Co-doped Zn1−xCdxS were facilely fabricated via adopting ZIFs as templates, and Cd(NO3)2 and thiourea as precursors. The highly porous microstructure and uniform Co-doping of the photocatalyst afford a high H2-production rate (45.2 and 422.2 times larger than those of Zn0.5Cd0.5S and CdS), providing an effective way for the development of high performance nanoporous photocatalysts.
Co-reporter:Yu-Jia Tang;Yu Wang;Xiao-Li Wang;Shun-Li Li;Wei Huang;Long-Zhang Dong;Chun-Hui Liu;Ya-Fei Li
Advanced Energy Materials 2016 Volume 6( Issue 12) pp:
Publication Date(Web):
DOI:10.1002/aenm.201600116
Facile design of low-cost and highly active catalysts from earth-abundant elements is favorable for the industrial application of water splitting. Here, a simple strategy to synthesize an ultrathin molybdenum disulfide/nitrogen-doped reduced graphene oxide (MoS2/N-RGO-180) nanocomposite with the enlarged interlayer spacing of 9.5 Å by a one-step hydrothermal method is reported. The synergistic effects between the layered MoS2 nanosheets and N-doped RGO films contribute to the high activity for hydrogen evolution reaction (HER). MoS2/N-RGO-180 exhibits the excellent catalytic activity with a low onset potential of −5 mV versus reversible hydrogen elelctrode (RHE), a small Tafel slope of 41.3 mV dec−1, a high exchange current density of 7.4 × 10−4 A cm−2, and good stability over 5 000 cycles under acidic conditions. The HER performance of MoS2/N-RGO-180 nanocomposite is superior to the most reported MoS2-based catalysts, especially its onset potential and exchange current density. In this work, a novel and simple method to the preparation of low-cost MoS2-based electrocatalysts with the extraordinary HER performance is presented.
Co-reporter:Jun-Sheng Qin; Dong-Ying Du; Mian Li; Xi-Zhen Lian; Long-Zhang Dong; Mathieu Bosch; Zhong-Min Su; Qiang Zhang; Shun-Li Li; Ya-Qian Lan; Shuai Yuan;Hong-Cai Zhou
Journal of the American Chemical Society 2016 Volume 138(Issue 16) pp:5299-5307
Publication Date(Web):April 5, 2016
DOI:10.1021/jacs.6b01093
Quests for advanced functionalities in metal–organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. In this paper, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building unit (SBU), {Zn4(tz)3}, was bridged by three TDC2– fragments to initially form a trigonal prismatic node, {Zn8(tz)6(TDC)3} (Htz = 1H-1,2,3-triazole and H2TDC = 2,5-thiophenedicarboxylic acid). Furthermore, the trigonal prism unit can be considered as a double SBU derived from triply bound triangular frusta. By considering theoretical derived nets for linking this trigonal-prismatic node with ditopic, tritopic, and tetratopic linkers, we have synthesized and characterized a new family of MOFs that adopt the decorated lon, jea, and xai nets, respectively. Pore sizes have also been successively increased within TPMOF-n family, which facilitates heterogeneous biomimetic catalysis with Fe–porphyrin-based TPMOF-7 as a catalyst.
Co-reporter:Ji-Sen Li, Yu-Jia Tang, Chun-Hui Liu, Shun-Li Li, Run-Han Li, Long-Zhang Dong, Zhi-Hui Dai, Jian-Chun Bao and Ya-Qian Lan
Journal of Materials Chemistry A 2016 vol. 4(Issue 4) pp:1202-1207
Publication Date(Web):16 Dec 2015
DOI:10.1039/C5TA09743F
The design and fabrication of electrocatalysts for HER, with superior activity and stability, still remain a significant challenge for clean and renewable energy technologies. Here we have synthesized Fe3C/Mo2C-containing N, P co-doped graphitic carbon derived from POM@MOF-100 (Fe) (denoted as Fe3C/Mo2C@NPGC) via a “killing three birds with one stone” strategy. The Fe3C/Mo2C@NPGC catalyst demonstrates excellent electrocatalytic activity and stability towards HER with a low onset overpotential of 18 mV (vs. RHE), small Tafel slope of 45.2 mV dec−1, as well as long-term durability for 10 h, which is one of the best non-noble metal HER catalysts in acidic media reported so far. Most importantly, this work opens up exciting opportunities for fabricating novel and highly efficient electrocatalysts to replace Pt or Pt-based catalysts utilizing POM-based metal–organic frameworks (MOFs) as precursors.
Co-reporter:Kui Li, Rong Chen, Shun-Li Li, Shuai-Lei Xie, Xue-Li Cao, Long-Zhang Dong, Jian-Chun Bao, and Ya-Qian Lan
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 7) pp:4516
Publication Date(Web):February 2, 2016
DOI:10.1021/acsami.5b11388
Heteronanomaterials composed of suitable semiconductors enable the direct conversion from solar power into clean and renewable energy. Ternary heterostructures with appropriate configuration and morphology possess rich and varied properties, especially for improving the photocatalytic activity and stability synchronously. However, suitable ternary heterostructure prototypes and facile while effective strategy for modulating their morphology and configuration are still scarce. Herein, various ternary ZnS-CdS-Zn1–xCdxS heterostructures with tunable morphology (0 to 2 D) and semiconductor configurations (randomly distributed, interface mediated, and quantum dots sensitized core@shell heterostructures) were facilely synthesized via one-pot hydrothermal method resulting from the different molecular structures of the amine solvents. Semiconductor morphology, especially configuration of the ternary heterostructure, shows dramatic effect on their photocatalytic activity. The CdS sensitized porous Zn1–xCdxS@ZnS core@shell takes full advantage of ZnS, Zn1–xCdxS and CdS and shows the maximal photocatalytic H2-production rate of 100.2 mmol/h/g and excellent stability over 30 h. This study provides some guidelines for the design and synthesis of high-performance ternary heterostructure via modulation of semiconductor configuration and morphology using one-pot method.Keywords: configuration; core−shell; morphology; photocatalytic activity; ternary heterostructure
Co-reporter:Wei Xie, Wen-Wen He, Dong-Ying Du, Shun-Li Li, Jun-Sheng Qin, Zhong-Min Su, Chun-Yi Sun and Ya-Qian Lan
Chemical Communications 2016 vol. 52(Issue 16) pp:3288-3291
Publication Date(Web):16 Dec 2015
DOI:10.1039/C5CC08703A
A stable mesoporous blue-emitting MOF NENU-521 was successfully constructed. NENU-521 can serve as a host for encapsulating Alq3 to obtain tunable and efficient white-light emission. The Alq3@NENU-521 composite possesses excellent stability and can be used as a promising white phosphor in WLEDs.
Co-reporter:Bing-Lei Hou, Dan Tian, Jiang Liu, Long-Zhang Dong, Shun-Li Li, Dong-Sheng Li, and Ya-Qian Lan
Inorganic Chemistry 2016 Volume 55(Issue 20) pp:10580-10586
Publication Date(Web):September 27, 2016
DOI:10.1021/acs.inorgchem.6b01809
A new metal–organic framework [Zn5(hfipbb)4(trz)2(H2O)2] (NNU-1) [H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid), Htrz = 1H-1,2,3-triazole] was assembled by hydrothermal synthesis. Single-crystal X-ray diffraction analysis reveals that NNU-1 displays a twofold interpenetrating three-dimensional (3D) framework with a {424·64}-bcu topology. Interestingly, the 3D framework contains a two-dimensional (2D) layered structure that consists of alternating left- and right-handed double helical chains. On the basis of the hydrophobic −CF3 groups from H2hfipbb ligand, NNU-1 possesses excellent stability in water. It is worth noting that NNU-1 not only shows a highly selective fluorescence quenching effect to Fe3+ ion in aqueous solution but also resists the interference of other metals including Fe2+ ion. Accordingly, NNU-1 probably functions as a potential promising fluorescence sensor for detecting Fe3+ ion with high sensitivity and selectivity.
Co-reporter:Rong Chen, Kui Li, Xiao-Shu Zhu, Shuai-Lei Xie, Long-Zhang Dong, Shun-Li Li and Ya-Qian Lan
CrystEngComm 2016 vol. 18(Issue 8) pp:1446-1452
Publication Date(Web):21 Jan 2016
DOI:10.1039/C5CE02420J
The in situ synthesis of ZnO-embedded Zn1−xCdxS/CdS heterostructure nanocrystals was achieved by using a simple surfactant-free hydrothermal route. The morphology and the exposed active site content of Zn1−xCdxS/CdS could be facilely modulated by varying the particle size of ZnS precursors, and the heterostructure with the smallest particle size showed the highest photocatalytic activity of 22.99 mmol h−1 g−1 in Na2S + Na2SO3 solution. Furthermore, the in situ embedding of the ZnO cocatalyst on the Zn1−xCdxS/CdS heterostructure dramatically improved its photocatalytic activity to 84.17 mmol h−1 g−1, which is 765 times higher than that of CdS prepared by a hydrothermal method. More significantly, the ZnO-embedded Zn1−xCdxS/CdS heterostructure gave a considerable H2 production rate even in the absence of hole scavengers, whereas the bare Zn1−xCdxS/CdS exhibited no hydrogen evolution, and it showed very competitive photocatalytic activity in methanol in comparison with that in Na2S + Na2SO3 solution under similar alkaline circumstances. These investigations indicate that the existence of the ZnO cocatalyst in the heterostructure could not only effectively improve the photocatalytic activity by suppressing the recombination of charge carriers and acting as a photocatalytic reaction site, but also make it possible to adopt methanol as the sacrificial reagent for sulfide photocatalysts.
Co-reporter:Ji-Sen Li, Hui-Qing Dong, Shun-Li Li, Run-Han Li, Zhi-Hui Dai, Jian-Chun Bao and Ya-Qian Lan
New Journal of Chemistry 2016 vol. 40(Issue 2) pp:914-918
Publication Date(Web):30 Jul 2015
DOI:10.1039/C5NJ01659B
A polyoxometalate (POM)-assisted fabrication of Pd nanoparticle/reduced graphene oxide (rGO) nanocomposite is reported. The hybrid exhibits enhanced catalytic activity and excellent methanol-tolerance capacity compared to its counterparts, due to the synergistic effect of Pd, POM, and rGO.
Co-reporter:Jun-Sheng Qin; Dong-Ying Du; Wei Guan; Xiang-Jie Bo; Ya-Fei Li; Li-Ping Guo; Zhong-Min Su; Yuan-Yuan Wang; Ya-Qian Lan;Hong-Cai Zhou
Journal of the American Chemical Society 2015 Volume 137(Issue 22) pp:7169-7177
Publication Date(Web):May 1, 2015
DOI:10.1021/jacs.5b02688
Two novel polyoxometalate (POM)-based metal–organic frameworks (MOFs), [TBA]3[ε-PMoV8MoVI4O36(OH)4Zn4][BTB]4/3·xGuest (NENU-500, BTB = benzene tribenzoate, TBA+ = tetrabutylammonium ion) and [TBA]3[ε-PMoV8MoVI4O37(OH)3Zn4][BPT] (NENU-501, BPT = [1,1′-biphenyl]-3,4′,5-tricarboxylate), were isolated. In these compounds, the POM fragments serving as nodes were directly connected with organic ligands giving rise to three-dimensional (3D) open frameworks. The two anionic frameworks were balanced by TBA+ ions residing inside the open channels. They exhibit not only good stability in air but also tolerance to acidic and basic media. Furthermore, they were employed as electrocatalysts for the hydrogen evolution reaction (HER) owing to the combination of the redox activity of a POM unit and the porosity of a MOF. Meanwhile, the HER activities of ε(trim)4/3, NENU-5, and HKUST-1 were also studied for comparison. Remarkably, as a 3D hydrogen-evolving cathode operating in acidic electrolytes, NENU-500 exhibits the highest activity among all MOF materials. It shows an onset overpotential of 180 mV and a Tafel slope of 96 mV·dec–1, and the catalytic current density can approach 10 mA·cm–2 at an overpotential of 237 mV. Moreover, NENU-500 and NENU-501 maintain their electrocatalytic activities after 2000 cycles.
Co-reporter:Kui Li, Rong Chen, Shun-Li Li, Min Han, Shuai-Lei Xie, Jian-Chun Bao, Zhi-Hui Dai and Ya-Qian Lan
Chemical Science 2015 vol. 6(Issue 9) pp:5263-5268
Publication Date(Web):18 Jun 2015
DOI:10.1039/C5SC01586C
We designed and successfully fabricated a ZnS/CdS 3D mesoporous heterostructure with a mediating Zn1−xCdxS interface that serves as a charge carrier transport channel for the first time. The H2-production rate and the stability of the heterostructure involving two sulfides were dramatically and simultaneously improved by the careful modification of the interface state via a simple post-annealing method. The sample prepared with the optimal parameters exhibited an excellent H2-production rate of 106.5 mmol h−1 g−1 under visible light, which was 152 and 966 times higher than CdS prepared using ethylenediamine and deionized water as the solvent, respectively. This excellent H2-production rate corresponded to the highest value among the CdS-based photocatalysts. Moreover, this heterostructure showed excellent photocatalytic stability over 60 h.
Co-reporter:Shao-Juan Bao, Rajamani Krishna, Ya-Bing He, Jun-Sheng Qin, Zhong-Min Su, Shun-Li Li, Wei Xie, Dong-Ying Du, Wen-Wen He, Shu-Ran Zhang and Ya-Qian Lan
Journal of Materials Chemistry A 2015 vol. 3(Issue 14) pp:7361-7367
Publication Date(Web):30 Jan 2015
DOI:10.1039/C5TA00256G
An air-stable tetrazolate-containing framework, [Zn2L2]·2DMF (NENU-520, H2L = 4-(1H-tetrazole-5-yl)biphenyl-4-carboxylic acid), with uncoordinated N atoms on its internal surface was solvothermally synthesized and structurally characterized. This metal–organic framework (MOF) exhibited high CO2 uptake of 79.9 cm3 cm−3 at 298 K and 100 kPa, as well as excellent adsorption selectivity for CO2 over CH4 and N2. Particularly, its exceptionally high selectivity of CO2 over N2 at 298 K has ranked NENU-520 among the highest MOFs for selective CO2 separation. Furthermore, the potential application of NENU-520 for the fixed bed pressure swing adsorption (PSA) separation of CO2 from CH4 and N2 has been validated via simulated breakthrough experiments. The small channel with the size of 3.6 Å, combined with CO2-accessible free nitrogen atoms directed toward the inner surface, is believed to contribute to its high CO2 uptake capacity and selectivity. Thus, this work represents a unique way to target MOF materials for highly selective CO2 separation by incorporating CO2-philic functional sites on pore surfaces, and at the same time optimizing pore sizes.
Co-reporter:Shu-Ran Zhang, Jing Li, Dong-Ying Du, Jun-Sheng Qin, Shun-Li Li, Wen-Wen He, Zhong-Min Su and Ya-Qian Lan
Journal of Materials Chemistry A 2015 vol. 3(Issue 46) pp:23426-23434
Publication Date(Web):12 Oct 2015
DOI:10.1039/C5TA07427D
In this work, a novel microporous anionic metal–organic framework (MOF), [Zn(ABTC)0.5(NO3)][(CH3)2NH2]·DMA·3H2O (NENU-505; NENU = Northeast Normal University; H4ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N,N-dimethylacetamide), has been rationally synthesized under solvothermal conditions. Single-crystal X-ray analysis reveals that NENU-505 is a (4,4)-connected 3D network with pts topology. Charge neutrality is achieved by [(CH3)2NH2]+ ions. It is noteworthy that NENU-505 displays high stability in air for more than two months. In particular, the adsorption ability of NENU-505 toward ionic dyes has been also investigated. According to the UV/vis spectroscopy analysis and the colour variance of NENU-505, we found that the cationic dyes could be efficiently adsorbed over a period of time, while the neutral and anionic dyes could not be adsorbed. Therefore, NENU-505 exhibits selective adsorption toward cationic dyes and can potentially serve as a column-chromatographic filler for the separation of dye molecules. Furthermore, the cationic dyes can be gradually released in the presence of NaCl. More interestingly, when NENU-505 was immersed in different metal ion DMA solutions, it performs as a rare example of a highly selective and sensitive sensor for Cr3+ ions. In connection to this, the probable sensing mechanism was also further investigated in detail in this paper. Remarkably, this is the first MOF to exhibit an excellent ability for the detection and adsorption of Cr3+ ions in a convenient, economical, and environmentally friendly manner.
Co-reporter:Ji-Sen Li, Shun-Li Li, Yu-Jia Tang, Min Han, Zhi-Hui Dai, Jian-Chun Bao and Ya-Qian Lan
Chemical Communications 2015 vol. 51(Issue 13) pp:2710-2713
Publication Date(Web):05 Jan 2015
DOI:10.1039/C4CC09062D
A novel nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrid derived from MOFs has been first fabricated by a facile approach. The hybrid exhibited outstanding bifunctional electrocatalytic activity for ORR and OER, due to the merits of graphitic layer/carbon nanotube structures with highly active N and Fe/Fe3C sites.
Co-reporter:Yuyun Chen, Min Han, Yujia Tang, Jianchun Bao, Shunli Li, Yaqian Lan and Zhihui Dai
Chemical Communications 2015 vol. 51(Issue 62) pp:12377-12380
Publication Date(Web):23 Jun 2015
DOI:10.1039/C5CC02717A
Novel polypyrrole–polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm−2), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.
Co-reporter:Jun-Sheng Qin;Ji-Chuan Zhang;Min Zhang;Dong-Ying Du;Jing Li;Zhong-Min Su;Yuan-Yuan Wang;Si-Ping Pang;Sheng-Hua Li
Advanced Science 2015 Volume 2( Issue 12) pp:
Publication Date(Web):
DOI:10.1002/advs.201500150
Co-reporter:Wei Xie; Shu-Ran Zhang; Dong-Ying Du; Jun-Sheng Qin; Shao-Juan Bao; Jing Li; Zhong-Min Su; Wen-Wen He; Qiang Fu
Inorganic Chemistry 2015 Volume 54(Issue 7) pp:3290-3296
Publication Date(Web):March 13, 2015
DOI:10.1021/ic5029383
A stable porous carbazole-based luminescent metal–organic framework, NENU-522, was successfully constructed. It is extremely stable in air and acidic/basic aqueous solutions, which provides the strategy for luminescent material encapsulation of Ln3+ ions with tunable luminescence for application in light emission. More importantly, Ln3+@NENU-522 can emit white light by encapsulating different molar ratios of Eu3+ and Tb3+ ions. Additionally, Tb3+@NENU-522 is found to be useful as a fluorescent indicator for the qualitative and quantitative detection of nitroaromatic explosives with different numbers of −NO2 groups, and the concentrations of complete quenching are about 2000, 1000, and 80 ppm for nitrobenzene, 1,3-dinitrobenzene, and 2,4,6-trinitrophenol, respectively. Meanwhile, Tb3+@NENU-522 displays high selectivity and recyclability in the detection of nitroaromatic explosives.
Co-reporter:Ji-Sen Li, Yu-Jia Tang, Shun-Li Li, Shu-Ran Zhang, Zhi-Hui Dai, Ling Si and Ya-Qian Lan
CrystEngComm 2015 vol. 17(Issue 5) pp:1080-1085
Publication Date(Web):24 Nov 2014
DOI:10.1039/C4CE02020K
Metal–organic frameworks (MOFs) hybrid composites, combining the advantages of both MOFs and nanoparticles, may exhibit unprecedented properties. Herein, carbon nanodots (Cdots) functional UMCM-1 composites (Cdots@UMCM-1a) were successfully synthesized by a stepwise synthetic approach for the first time. The hybrids retain the intact structure of MOFs with high luminescence and longer stability. Due to the interactions between polar functional groups at the surface of the Cdots and H2 molecules, Cdots@UMCM-1a efficiently enhanced H2 storage capacity. Most importantly, Cdots@UMCM-1a exhibited highly fluorescent sensing for nitroaromatic explosives owing to the double effect of porous MOFs and fluorescent Cdots. This work will pave new avenues for the fabrication of novel and multifunctional MOFs composites.
Co-reporter:Dr. Yu-Jia Tang;Dr. Min-Rui Gao;Dr. Chun-Hui Liu; Shun-Li Li; Hai-Long Jiang; Ya-Qian Lan; Min Han; Shu-Hong Yu
Angewandte Chemie International Edition 2015 Volume 54( Issue 44) pp:12928-12932
Publication Date(Web):
DOI:10.1002/anie.201505691
Abstract
We have synthesized a porous Mo-based composite obtained from a polyoxometalate-based metal–organic framework and graphene oxide (POMOFs/GO) using a simple one-pot method. The MoO2@PC-RGO hybrid material derived from the POMOFs/GO composite is prepared at a relatively low carbonization temperature, which presents a superior activity for the hydrogen-evolution reaction (HER) in acidic media owing to the synergistic effects among highly dispersive MoO2 particles, phosphorus-doped porous carbon, and RGO substrates. MoO2@PC-RGO exhibits a very positive onset potential close to that of 20 % Pt/C, low Tafel slope of 41 mV dec−1, high exchange current density of 4.8×10−4 A cm−2, and remarkable long-term cycle stability. It is one of the best high-performance catalysts among the reported nonprecious metal catalysts for HER to date.
Co-reporter:Dr. Yu-Jia Tang;Dr. Min-Rui Gao;Dr. Chun-Hui Liu; Shun-Li Li; Hai-Long Jiang; Ya-Qian Lan; Min Han; Shu-Hong Yu
Angewandte Chemie 2015 Volume 127( Issue 44) pp:13120-13124
Publication Date(Web):
DOI:10.1002/ange.201505691
Abstract
We have synthesized a porous Mo-based composite obtained from a polyoxometalate-based metal–organic framework and graphene oxide (POMOFs/GO) using a simple one-pot method. The MoO2@PC-RGO hybrid material derived from the POMOFs/GO composite is prepared at a relatively low carbonization temperature, which presents a superior activity for the hydrogen-evolution reaction (HER) in acidic media owing to the synergistic effects among highly dispersive MoO2 particles, phosphorus-doped porous carbon, and RGO substrates. MoO2@PC-RGO exhibits a very positive onset potential close to that of 20 % Pt/C, low Tafel slope of 41 mV dec−1, high exchange current density of 4.8×10−4 A cm−2, and remarkable long-term cycle stability. It is one of the best high-performance catalysts among the reported nonprecious metal catalysts for HER to date.
Co-reporter:Dong-Ying Du, Jun-Sheng Qin, Shun-Li Li, Zhong-Min Su and Ya-Qian Lan
Chemical Society Reviews 2014 vol. 43(Issue 13) pp:4615-4632
Publication Date(Web):27 Mar 2014
DOI:10.1039/C3CS60404G
Polyoxometalate (POM)-based metal–organic framework (MOF) materials contain POM units and generally generate MOF materials with open networks. POM-based MOF materials, which utilize the advantages of both POMs and MOFs, have received increasing attention, and much effort has been devoted to their preparation and relevant applications over the past few decades. They have good prospects in catalysis owing to the electronic and physical properties of POMs that are tunable by varying constituent elements. In this review, we present recent developments in porous POM-based MOF materials, including their classification, synthesis strategies, and applications, especially in the field of catalysis.
Co-reporter:Wen-Wen He, Shun-Li Li, Hong-Ying Zang, Guang-Sheng Yang, Shu-Ran Zhang, Zhong-Min Su, Ya-Qian Lan
Coordination Chemistry Reviews 2014 Volume 279() pp:141-160
Publication Date(Web):1 November 2014
DOI:10.1016/j.ccr.2014.03.022
•We have reviewed a good number of POM-based coordination polymers with entangled structures.•Different topological concepts are employed to describe the various types of these polymers.•Further classification is based on the dimensionalities of the individual motifs and the roles of the POMs.•The unique characteristics of the POMs make them perfect templates and linkers in the formation of these structures.Polyoxometalates (POMs) have attracted a lot of interest due to their novel structure characteristics and various connection modes. POM-based coordination polymers with entangled structures, an indispensable branch of entangled networks, take advantage of the features of POMs, and have received increasing attention. Much effort has been devoted over the past few decades toward their preparation and the analysis of their unusual entangled topology. In this review, we will summarize a number of examples of POM-based coordination polymer that have been described according to their different entangled characteristics. Different concepts, such as interpenetration, polycatenation, polyrotaxane, polypseudo-rotaxane and self-penetration, are employed to describe the various types of POM-based coordination polymers with entangled structures. In addition, we further classify POM-based coordination polymers with entangled structures based on the dimensionalities of the individual motifs and the roles of the POMs. Combining the advantages of the attractive potential applications of the POMs and structure diversities of the entangled frameworks, the investigation of POM-based coordination polymers with entangled structures will be a sustainable research field in coordination chemistry.
Co-reporter:Ping Shen, Wen-Wen He, Dong-Ying Du, Hai-Long Jiang, Shun-Li Li, Zhong-Ling Lang, Zhong-Min Su, Qiang Fu and Ya-Qian Lan
Chemical Science 2014 vol. 5(Issue 4) pp:1368-1374
Publication Date(Web):02 Dec 2013
DOI:10.1039/C3SC52666F
In this work, we have demonstrated an unprecedented single-crystal-to-single-crystal (SCSC) transformation between two 3D metal-organic frameworks (MOFs). The centrosymmetric IFMC-68 ([(Zn4O)2(L)3]·10H2O·46DMA) transforms into a chiral IFMC-69 ([(Zn4O)2(L)3H2O]·H2O·4DMA) doubly triggered by reaction temperature and time simultaneously in the presence or absence of solvent. To our knowledge, this is the first representative that the non-interpenetrated structure transforms into self-penetrated structure in MOFs. For the first time, we have studied the influence of reaction temperature and time on SCSC transformation, simultaneously, and get the transformation relationship among IFMC-68, IFMC-69 and the intermediate coming from the direct synthesis method and stepwise synthesis method at different temperatures and for different times. Meanwhile, we have achieved the conversion from an air-unstable to air-stable structure. Air-stable IFMC-69 exhibits the selective CO2 uptake over N2 and more excellent gas adsorption ability than IFMC-68. In addition, IFMC-69 shows an efficient capability in reversible adsorption of iodine. The electrical conductivity value (σ) of I2@IFMC-69 is much higher than the pristine MOF and thus is promising for potential semiconductor materials in the future.
Co-reporter:Jisen Li, Yuyun Chen, Yujia Tang, Shunli Li, Huiqing Dong, Kui Li, Min Han, Ya-Qian Lan, Jianchun Bao and Zhihui Dai
Journal of Materials Chemistry A 2014 vol. 2(Issue 18) pp:6316-6319
Publication Date(Web):29 Jan 2014
DOI:10.1039/C3TA15335E
A novel MOF-templated nitrogen and sulphur co-doped porous material has been synthesized as an efficient electrocatalyst for oxygen reduction reactions (ORRs) for the first time. The representative NS(3:1)–C-MOF-5 catalyst shows the highest onset potential, and is even comparable to commercial Pt–C catalyst, due to the synergistic effect of N and S co-doping.
Co-reporter:Hui-Qing Dong, Yu-Yun Chen, Min Han, Shun-Li Li, Jie Zhang, Ji-Sen Li, Ya-Qian Lan, Zhi-Hui Dai and Jian-Chun Bao
Journal of Materials Chemistry A 2014 vol. 2(Issue 5) pp:1272-1276
Publication Date(Web):13 Nov 2013
DOI:10.1039/C3TA13585C
We synthesized a novel mesoporous Mn2O3 nanostructure as an electrocatalyst support, then Pd–Mn2O3 with different Pd loading amounts were obtained by a facile solvothermal method. The Pd–Mn2O3 demonstrated a good competitive ORR activity and a high selectivity in alkaline medium, which can be comparable to commercial Pt/C catalysts.
Co-reporter:Shu-Ran Zhang, Dong-Ying Du, Jun-Sheng Qin, Shun-Li Li, Wen-Wen He, Ya-Qian Lan, and Zhong-Min Su
Inorganic Chemistry 2014 Volume 53(Issue 15) pp:8105-8113
Publication Date(Web):July 23, 2014
DOI:10.1021/ic5011083
In this work, five novel 2D isostructural Cd(II)–lanthanide(III) heterometallic–organic frameworks [CdCl(L)EuxTby(H2O)(DMA)](NO3)·3DMA (IFMC-36-EuxTby: x = 1, y = 0, IFMC-36-Eu; x = 0.6, y = 0.4, IFMC-36-Eu0.6Tb0.4; x = 0.5, y = 0.5, IFMC-36-Eu0.5Tb0.5; x = 0.4, y = 0.6, IFMC-36-Eu0.4Tb0.6; x = 0, y = 1, IFMC-36-Tb; H3L is 4,4′,4″-((2,2′,2″-(nitrilotris(methylene))tris(1H-benzo[d]imidazole-2,1-diyl))tris(methylene))tribenzoic acid; IFMC = Institute of Functional Material Chemistry) have been successfully synthesized by taking advantage of different molar ratios of lanthanide(III) (Ln(III)) and metalloligands under solvothermal conditions. Further luminescent measurements indicate that IFMC-36-EuxTby exhibits characteristic sharp emission bands of Eu(III) and Tb(III), and the intensities of red and green can be modulated correspondingly by tuning the ratios of Eu(III) and Tb(III). Particularly, the solvent-dependent luminescent behavior of IFMC-36-Eu shows a potential application in detection of small-molecule pollutant nitrobenzene by significant fluorescence quenching. Furthermore, IFMC-36-Eu displays preeminent anti-interference ability and could be used for sensing in the systems with complicated components. This is the first time that a d–f heterometallic–organic framework can be investigated as a chemical sensor for selective, sensitive, and recyclable detection of nitrobenzene.
Co-reporter:Dr. Jun-Sheng Qin;Dr. Shu-Ran Zhang;Dr. Dong-Ying Du;Ping Shen;Shao-Juan Bao; Ya-Qian Lan; Zhong-Min Su
Chemistry - A European Journal 2014 Volume 20( Issue 19) pp:5625-5630
Publication Date(Web):
DOI:10.1002/chem.201304480
Abstract
Herein, a novel anionic framework with primitive centered cubic (pcu) topology, [(CH3)2NH2]4[(Zn4dttz6)Zn3]⋅15 DMF⋅4.5 H2O, (IFMC-2; H3dttz=4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole) was solvothermally isolated. A new example of a tetranuclear zinc cluster {Zn4dttz6} served as a secondary building unit in IFMC-2. Furthermore, the metal cluster was connected by ZnII ions to give rise to a 3D open microporous structure. The lanthanide(III)-loaded metal–organic framework (MOF) materials Ln3+@IFMC-2, were successfully prepared by using ion-exchange experiments owing to the anionic framework of IFMC-2. Moreover, the emission spectra of the as-prepared Ln3+@IFMC-2 were investigated, and the results suggested that IFMC-2 could be utilized as a potential luminescent probe toward different Ln3+ ions. Additionally, the absorption ability of IFMC-2 toward ionic dyes was also performed. Cationic dyes can be absorbed, but not neutral and anionic dyes, thus indicating that IFMC-2 exhibits selective absorption toward cationic dyes. Furthermore, the cationic dyes can be gradually released in the presence of NaCl.
Co-reporter:Dr. Jun-Sheng Qin;Shao-Juan Bao;Dr. Peng Li;Wei Xie;Dr. Dong-Ying Du;Dr. Liang Zhao; Ya-Qian Lan; Zhong-Min Su
Chemistry – An Asian Journal 2014 Volume 9( Issue 3) pp:749-753
Publication Date(Web):
DOI:10.1002/asia.201301531
Abstract
A hexagonal channel-based porous anionic metal–organic framework was successfully constructed. IFMC-3 is stable in air and acidic/basic aqueous solutions at room temperature, and constitutes a selective luminescent sensing material for Ln3+ ions and a recyclable probe for the sensitive detection of nitrobenzene.
Co-reporter:Dr. Jun-Sheng Qin;Shao-Juan Bao;Dr. Peng Li;Wei Xie;Dr. Dong-Ying Du;Dr. Liang Zhao; Ya-Qian Lan; Zhong-Min Su
Chemistry – An Asian Journal 2014 Volume 9( Issue 3) pp:
Publication Date(Web):
DOI:10.1002/asia.201490005
Co-reporter:Dr. Shu-Ran Zhang;Dr. Dong-Ying Du;Dr. Jun-Sheng Qin;Dr. Shao-Juan Bao; Shun-Li Li;Dr. Wen-Wen He; Ya-Qian Lan;Dr. Ping Shen; Zhong-Min Su
Chemistry - A European Journal 2014 Volume 20( Issue 13) pp:3589-3594
Publication Date(Web):
DOI:10.1002/chem.201304692
Abstract
A 2D, extremely stable, metal–organic framework (MOF), NENU-503, was successfully constructed. It displays highly selective and recyclable properties in detection of nitroaromatic explosives as a fluorescent sensor. This is the first MOF that can distinguish between nitroaromatic molecules with different numbers of NO2 groups.
Co-reporter:Wen-Wen He, Shun-Li Li, Wen-Liang Li, Ji-Sen Li, Guang-Sheng Yang, Shu-Ran Zhang, Ya-Qian Lan, Ping Shen and Zhong-Min Su
Journal of Materials Chemistry A 2013 vol. 1(Issue 37) pp:11111-11116
Publication Date(Web):25 Jul 2013
DOI:10.1039/C3TA12662E
A novel microporous metal–organic framework, IFMC-16, has been successfully constructed by using mixed ligands. IFMC-16 has multipoint interaction sites and exhibits high hydrogen storage capacity not only at ambient pressure, but also at lower pressure in a high pressure region, and displays high adsorptive efficiency in the removal of organosulfur compounds.
Co-reporter:Dr. Shu-Ran Zhang;Dr. Dong-Ying Du; Ke Tan;Dr. Jun-Sheng Qin;Dr. Hui-Qing Dong; Shun-Li Li;Dr. Wen-Wen He; Ya-Qian Lan;Dr. Ping Shen; Zhong-Min Su
Chemistry - A European Journal 2013 Volume 19( Issue 34) pp:11279-11286
Publication Date(Web):
DOI:10.1002/chem.201301536
Abstract
A new family of heterometal–organic frameworks has been prepared by two synthesis strategies, in which IFMC-26 and IFMC-27 are constructed by self-assembly and IFMC-28 is obtained by stepwise synthesis based on the metalloligand (IFMC=Institute of Functional Material Chemistry). IFMC-26 is a (3,6)-connected net and IFMC-27 is a (4,8)-connected 3D framework. The metalloligands {Ni(H4L)}(NO3)2 are connected by binuclear lanthanide clusters giving rise to a 2D sheet structure in IFMC-28. Notably, IFMC-26-EuxTby and IFMC-28-EuxTby have been obtained by changing the molar ratios of raw materials. Owing to the porosity of IFMC-26, Tb3+@IFMC-26-Eu and Eu3+@IFMC-26-Tb are obtained by postencapsulating TbIII and EuIII ions into the pores, respectively. Tunable luminescence in metal–organic frameworks is achieved by the two kinds of doping methods. In particular, the quantum yields of heterometal–organic frameworks are apparently enhanced by postencapsulation of LnIII ions.
Co-reporter:Tao Wei, Mi Zhang, Ping Wu, Yu-Jia Tang, Shun-Li Li, Feng-Cui Shen, Xiao-Li Wang, Xin-Ping Zhou, Ya-Qian Lan
Nano Energy (April 2017) Volume 34() pp:
Publication Date(Web):April 2017
DOI:10.1016/j.nanoen.2017.02.028
•PMG nanocomposite is used as an anode material for lithium-ion batteries for the first time.•PMG nanocomposite demonstrates the hybrid behavior of battery and supercapacitor.•Its capacity and rate performances are almost the best compared to the reported pristine MOFs and POMs based materials.The energy storage field has witnessed a dramatic expansion in research at materials that might combine the high energy density of batteries and short charging times of supercapacitors. However, the materials mainly focus on transition metal oxides or sulfides, new material has rarely been reported yet. Herein, we report a novel nanocomposite based on polyoxometalates-based metal–organic frameworks (POMOFs)/reduced graphene oxide (RGO) for lithium-ion batteries. It demonstrates the advantages of polyoxometalates (POMs), metal–organic frameworks (MOFs) and RGO, thus shows the hybrid behavior of battery and supercapacitor. A reversible capacity of 1075 mAh g−1 was maintained after 100 cycles, and the capacity retentions are nearly 100% both at 2000 and 3000 mA g−1 for over 400 cycles. These performances are almost the best compared to the reported pristine MOFs and POMs based materials to date. The design and synthesis of POMOFs/RGO nanocomposites might guide the development of new generation electrode materials for lithium-ion batteries.
Co-reporter:Wen-Wen He, Shun-Li Li, Wen-Liang Li, Ji-Sen Li, Guang-Sheng Yang, Shu-Ran Zhang, Ya-Qian Lan, Ping Shen and Zhong-Min Su
Journal of Materials Chemistry A 2013 - vol. 1(Issue 37) pp:NaN11116-11116
Publication Date(Web):2013/07/25
DOI:10.1039/C3TA12662E
A novel microporous metal–organic framework, IFMC-16, has been successfully constructed by using mixed ligands. IFMC-16 has multipoint interaction sites and exhibits high hydrogen storage capacity not only at ambient pressure, but also at lower pressure in a high pressure region, and displays high adsorptive efficiency in the removal of organosulfur compounds.
Co-reporter:Wei Xie, Jun-Sheng Qin, Wen-Wen He, Kui-Zhan Shao, Zhong-Min Su, Dong-Ying Du, Shun-Li Li and Ya-Qian Lan
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 3) pp:NaN552-552
Publication Date(Web):2017/01/12
DOI:10.1039/C6QI00528D
We successfully synthesized a novel anionic luminescent metal–organic framework (MOF) (NENU-524) with a lonsdaleite topology. NENU-524 contains a trigonal prismatic unit {Zn8(btca)6(2-NH2-bdc)3} that can be regarded as a double secondary building unit with an unusual triply bound triangular frustum geometry. The prepared NENU-524 had a permanent porosity and excellent stability in air. NENU-524 was used as a platform to encapsulate yellow-emitting [Ir(ppy)2(bpy)]+ cations in the nanotube channels of the blue-emitting MOF via an ion-exchange process. The [Ir(ppy)2(bpy)]+@NENU-524 MOF ([Ir(ppy)2(bpy)]+ concentration 3.86 wt%) emitted a pure white light with CIE coordinates of (0.300, 0.336) and a high quantum yield of up to 15.2%. The white light-emitting diodes assembled using [Ir(ppy)2(bpy)]+@NENU-524 as a white phosphor emitted a bright white light, suggesting that the composite is a promising material for use in lighting. The assembled white light-emitting diodes continued to emit a bright white light for up to one month. This simple and feasible approach could be used to develop luminescent luminophor@MOFs composites for practical applications.
Co-reporter:Yuan-Yuan Wang, Mi Zhang, Shun-Li Li, Shu-Ran Zhang, Wei Xie, Jun-Sheng Qin, Zhong-Min Su and Ya-Qian Lan
Chemical Communications 2017 - vol. 53(Issue 37) pp:NaN5207-5207
Publication Date(Web):2017/04/18
DOI:10.1039/C6CC10208E
Two novel isostructural polyoxometalate (POM)-based metal–organic frameworks (MOFs) with diamond topology, NENU-506 and NENU-507, were hydrothermally synthesized. They not only combine the advantages of both POMs and MOFs, but also show excellent chemical and thermal stability. Notably, NENU-507 exhibited a high reversible capacity of 640 mA h g−1 after 100 cycles when applied as an anode material in lithium-ion batteries.
Co-reporter:Wei Xie, Jun-Sheng Qin, Wen-Wen He, Kui-Zhan Shao, Zhong-Min Su, Dong-Ying Du, Shun-Li Li and Ya-Qian Lan
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 3) pp:NaN552-552
Publication Date(Web):2017/01/12
DOI:10.1039/C6QI00528D
We successfully synthesized a novel anionic luminescent metal–organic framework (MOF) (NENU-524) with a lonsdaleite topology. NENU-524 contains a trigonal prismatic unit {Zn8(btca)6(2-NH2-bdc)3} that can be regarded as a double secondary building unit with an unusual triply bound triangular frustum geometry. The prepared NENU-524 had a permanent porosity and excellent stability in air. NENU-524 was used as a platform to encapsulate yellow-emitting [Ir(ppy)2(bpy)]+ cations in the nanotube channels of the blue-emitting MOF via an ion-exchange process. The [Ir(ppy)2(bpy)]+@NENU-524 MOF ([Ir(ppy)2(bpy)]+ concentration 3.86 wt%) emitted a pure white light with CIE coordinates of (0.300, 0.336) and a high quantum yield of up to 15.2%. The white light-emitting diodes assembled using [Ir(ppy)2(bpy)]+@NENU-524 as a white phosphor emitted a bright white light, suggesting that the composite is a promising material for use in lighting. The assembled white light-emitting diodes continued to emit a bright white light for up to one month. This simple and feasible approach could be used to develop luminescent luminophor@MOFs composites for practical applications.
Co-reporter:Yuyun Chen, Min Han, Yujia Tang, Jianchun Bao, Shunli Li, Yaqian Lan and Zhihui Dai
Chemical Communications 2015 - vol. 51(Issue 62) pp:NaN12380-12380
Publication Date(Web):2015/06/23
DOI:10.1039/C5CC02717A
Novel polypyrrole–polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm−2), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.
Co-reporter:Wei Xie, Wen-Wen He, Dong-Ying Du, Shun-Li Li, Jun-Sheng Qin, Zhong-Min Su, Chun-Yi Sun and Ya-Qian Lan
Chemical Communications 2016 - vol. 52(Issue 16) pp:NaN3291-3291
Publication Date(Web):2015/12/16
DOI:10.1039/C5CC08703A
A stable mesoporous blue-emitting MOF NENU-521 was successfully constructed. NENU-521 can serve as a host for encapsulating Alq3 to obtain tunable and efficient white-light emission. The Alq3@NENU-521 composite possesses excellent stability and can be used as a promising white phosphor in WLEDs.
Co-reporter:Ji-Sen Li, Shun-Li Li, Yu-Jia Tang, Min Han, Zhi-Hui Dai, Jian-Chun Bao and Ya-Qian Lan
Chemical Communications 2015 - vol. 51(Issue 13) pp:NaN2713-2713
Publication Date(Web):2015/01/05
DOI:10.1039/C4CC09062D
A novel nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrid derived from MOFs has been first fabricated by a facile approach. The hybrid exhibited outstanding bifunctional electrocatalytic activity for ORR and OER, due to the merits of graphitic layer/carbon nanotube structures with highly active N and Fe/Fe3C sites.
Co-reporter:Kui Li, Rong Chen, Shun-Li Li, Min Han, Shuai-Lei Xie, Jian-Chun Bao, Zhi-Hui Dai and Ya-Qian Lan
Chemical Science (2010-Present) 2015 - vol. 6(Issue 9) pp:NaN5268-5268
Publication Date(Web):2015/06/18
DOI:10.1039/C5SC01586C
We designed and successfully fabricated a ZnS/CdS 3D mesoporous heterostructure with a mediating Zn1−xCdxS interface that serves as a charge carrier transport channel for the first time. The H2-production rate and the stability of the heterostructure involving two sulfides were dramatically and simultaneously improved by the careful modification of the interface state via a simple post-annealing method. The sample prepared with the optimal parameters exhibited an excellent H2-production rate of 106.5 mmol h−1 g−1 under visible light, which was 152 and 966 times higher than CdS prepared using ethylenediamine and deionized water as the solvent, respectively. This excellent H2-production rate corresponded to the highest value among the CdS-based photocatalysts. Moreover, this heterostructure showed excellent photocatalytic stability over 60 h.
Co-reporter:Ping Shen, Wen-Wen He, Dong-Ying Du, Hai-Long Jiang, Shun-Li Li, Zhong-Ling Lang, Zhong-Min Su, Qiang Fu and Ya-Qian Lan
Chemical Science (2010-Present) 2014 - vol. 5(Issue 4) pp:NaN1374-1374
Publication Date(Web):2013/12/02
DOI:10.1039/C3SC52666F
In this work, we have demonstrated an unprecedented single-crystal-to-single-crystal (SCSC) transformation between two 3D metal-organic frameworks (MOFs). The centrosymmetric IFMC-68 ([(Zn4O)2(L)3]·10H2O·46DMA) transforms into a chiral IFMC-69 ([(Zn4O)2(L)3H2O]·H2O·4DMA) doubly triggered by reaction temperature and time simultaneously in the presence or absence of solvent. To our knowledge, this is the first representative that the non-interpenetrated structure transforms into self-penetrated structure in MOFs. For the first time, we have studied the influence of reaction temperature and time on SCSC transformation, simultaneously, and get the transformation relationship among IFMC-68, IFMC-69 and the intermediate coming from the direct synthesis method and stepwise synthesis method at different temperatures and for different times. Meanwhile, we have achieved the conversion from an air-unstable to air-stable structure. Air-stable IFMC-69 exhibits the selective CO2 uptake over N2 and more excellent gas adsorption ability than IFMC-68. In addition, IFMC-69 shows an efficient capability in reversible adsorption of iodine. The electrical conductivity value (σ) of I2@IFMC-69 is much higher than the pristine MOF and thus is promising for potential semiconductor materials in the future.
Co-reporter:Shao-Juan Bao, Rajamani Krishna, Ya-Bing He, Jun-Sheng Qin, Zhong-Min Su, Shun-Li Li, Wei Xie, Dong-Ying Du, Wen-Wen He, Shu-Ran Zhang and Ya-Qian Lan
Journal of Materials Chemistry A 2015 - vol. 3(Issue 14) pp:NaN7367-7367
Publication Date(Web):2015/01/30
DOI:10.1039/C5TA00256G
An air-stable tetrazolate-containing framework, [Zn2L2]·2DMF (NENU-520, H2L = 4-(1H-tetrazole-5-yl)biphenyl-4-carboxylic acid), with uncoordinated N atoms on its internal surface was solvothermally synthesized and structurally characterized. This metal–organic framework (MOF) exhibited high CO2 uptake of 79.9 cm3 cm−3 at 298 K and 100 kPa, as well as excellent adsorption selectivity for CO2 over CH4 and N2. Particularly, its exceptionally high selectivity of CO2 over N2 at 298 K has ranked NENU-520 among the highest MOFs for selective CO2 separation. Furthermore, the potential application of NENU-520 for the fixed bed pressure swing adsorption (PSA) separation of CO2 from CH4 and N2 has been validated via simulated breakthrough experiments. The small channel with the size of 3.6 Å, combined with CO2-accessible free nitrogen atoms directed toward the inner surface, is believed to contribute to its high CO2 uptake capacity and selectivity. Thus, this work represents a unique way to target MOF materials for highly selective CO2 separation by incorporating CO2-philic functional sites on pore surfaces, and at the same time optimizing pore sizes.
Co-reporter:Shu-Ran Zhang, Jing Li, Dong-Ying Du, Jun-Sheng Qin, Shun-Li Li, Wen-Wen He, Zhong-Min Su and Ya-Qian Lan
Journal of Materials Chemistry A 2015 - vol. 3(Issue 46) pp:NaN23434-23434
Publication Date(Web):2015/10/12
DOI:10.1039/C5TA07427D
In this work, a novel microporous anionic metal–organic framework (MOF), [Zn(ABTC)0.5(NO3)][(CH3)2NH2]·DMA·3H2O (NENU-505; NENU = Northeast Normal University; H4ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N,N-dimethylacetamide), has been rationally synthesized under solvothermal conditions. Single-crystal X-ray analysis reveals that NENU-505 is a (4,4)-connected 3D network with pts topology. Charge neutrality is achieved by [(CH3)2NH2]+ ions. It is noteworthy that NENU-505 displays high stability in air for more than two months. In particular, the adsorption ability of NENU-505 toward ionic dyes has been also investigated. According to the UV/vis spectroscopy analysis and the colour variance of NENU-505, we found that the cationic dyes could be efficiently adsorbed over a period of time, while the neutral and anionic dyes could not be adsorbed. Therefore, NENU-505 exhibits selective adsorption toward cationic dyes and can potentially serve as a column-chromatographic filler for the separation of dye molecules. Furthermore, the cationic dyes can be gradually released in the presence of NaCl. More interestingly, when NENU-505 was immersed in different metal ion DMA solutions, it performs as a rare example of a highly selective and sensitive sensor for Cr3+ ions. In connection to this, the probable sensing mechanism was also further investigated in detail in this paper. Remarkably, this is the first MOF to exhibit an excellent ability for the detection and adsorption of Cr3+ ions in a convenient, economical, and environmentally friendly manner.
Co-reporter:Dong-Ying Du, Jun-Sheng Qin, Shun-Li Li, Zhong-Min Su and Ya-Qian Lan
Chemical Society Reviews 2014 - vol. 43(Issue 13) pp:NaN4632-4632
Publication Date(Web):2014/03/27
DOI:10.1039/C3CS60404G
Polyoxometalate (POM)-based metal–organic framework (MOF) materials contain POM units and generally generate MOF materials with open networks. POM-based MOF materials, which utilize the advantages of both POMs and MOFs, have received increasing attention, and much effort has been devoted to their preparation and relevant applications over the past few decades. They have good prospects in catalysis owing to the electronic and physical properties of POMs that are tunable by varying constituent elements. In this review, we present recent developments in porous POM-based MOF materials, including their classification, synthesis strategies, and applications, especially in the field of catalysis.
Co-reporter:Jiang Liu, Tian-Yi Bao, Xi-Ya Yang, Pei-Pei Zhu, Lian-He Wu, Jing-Quan Sha, Lei Zhang, Long-Zhang Dong, Xue-Li Cao and Ya-Qian Lan
Chemical Communications 2017 - vol. 53(Issue 55) pp:NaN7807-7807
Publication Date(Web):2017/06/19
DOI:10.1039/C7CC03673F
Two extremely rare β-cyclodextrin (β-CD) supported metal-organic frameworks (MOFs), CD-MOF-1 and CD-MOF-2, were induced to crystallize for the first time through a template-induced approach. The targeted CD-MOFs were employed to perform controlled drug delivery and cytotoxicity assays that confirmed their favourable biological potential of being used as drug carriers.
Co-reporter:Ji-Sen Li, Yu-Jia Tang, Chun-Hui Liu, Shun-Li Li, Run-Han Li, Long-Zhang Dong, Zhi-Hui Dai, Jian-Chun Bao and Ya-Qian Lan
Journal of Materials Chemistry A 2016 - vol. 4(Issue 4) pp:NaN1207-1207
Publication Date(Web):2015/12/16
DOI:10.1039/C5TA09743F
The design and fabrication of electrocatalysts for HER, with superior activity and stability, still remain a significant challenge for clean and renewable energy technologies. Here we have synthesized Fe3C/Mo2C-containing N, P co-doped graphitic carbon derived from POM@MOF-100 (Fe) (denoted as Fe3C/Mo2C@NPGC) via a “killing three birds with one stone” strategy. The Fe3C/Mo2C@NPGC catalyst demonstrates excellent electrocatalytic activity and stability towards HER with a low onset overpotential of 18 mV (vs. RHE), small Tafel slope of 45.2 mV dec−1, as well as long-term durability for 10 h, which is one of the best non-noble metal HER catalysts in acidic media reported so far. Most importantly, this work opens up exciting opportunities for fabricating novel and highly efficient electrocatalysts to replace Pt or Pt-based catalysts utilizing POM-based metal–organic frameworks (MOFs) as precursors.
Co-reporter:Hui-Qing Dong, Yu-Yun Chen, Min Han, Shun-Li Li, Jie Zhang, Ji-Sen Li, Ya-Qian Lan, Zhi-Hui Dai and Jian-Chun Bao
Journal of Materials Chemistry A 2014 - vol. 2(Issue 5) pp:NaN1276-1276
Publication Date(Web):2013/11/13
DOI:10.1039/C3TA13585C
We synthesized a novel mesoporous Mn2O3 nanostructure as an electrocatalyst support, then Pd–Mn2O3 with different Pd loading amounts were obtained by a facile solvothermal method. The Pd–Mn2O3 demonstrated a good competitive ORR activity and a high selectivity in alkaline medium, which can be comparable to commercial Pt/C catalysts.
Co-reporter:Jisen Li, Yuyun Chen, Yujia Tang, Shunli Li, Huiqing Dong, Kui Li, Min Han, Ya-Qian Lan, Jianchun Bao and Zhihui Dai
Journal of Materials Chemistry A 2014 - vol. 2(Issue 18) pp:NaN6319-6319
Publication Date(Web):2014/01/29
DOI:10.1039/C3TA15335E
A novel MOF-templated nitrogen and sulphur co-doped porous material has been synthesized as an efficient electrocatalyst for oxygen reduction reactions (ORRs) for the first time. The representative NS(3:1)–C-MOF-5 catalyst shows the highest onset potential, and is even comparable to commercial Pt–C catalyst, due to the synergistic effect of N and S co-doping.
Co-reporter:Qing Huang, Tao Wei, Mi Zhang, Long-Zhang Dong, A-Man Zhang, Shun-Li Li, Wen-Jing Liu, Jiang Liu and Ya-Qian Lan
Journal of Materials Chemistry A 2017 - vol. 5(Issue 18) pp:NaN8483-8483
Publication Date(Web):2017/04/06
DOI:10.1039/C7TA00900C
A novel polyoxometalate-based metal–organic framework (POMOF), [PMo8VMo4VIO37(OH)3Zn4][TPT]5·2TPT·2H2O (NNU-11, TPT = tris-(4-pyridyl)triazine), was synthesized. Zn-ε-Keggin fragments were directly connected with TPT ligands generating 2D layers and further interdigitated with each other by π–π stacking interactions to pack into a 3D array. The compound exhibited excellent stability in air and different organic solvents and even in different pH (pH 1–11) aqueous solutions. It can be utilized as an anode material for lithium ion batteries (LIBs) due to the combination of the multi-electron redox property of POM units and the functionalization of MOFs. NNU-11 exhibited a highly reversible capacity of 750 mA h g−1 at a current density of 50 mA g−1 after 200 cycles along with excellent cycle stability and rate performance. More importantly, for the first time, we designed and synthesized a POMOF crystalline structure model supported by π–π stacking interactions to demonstrate that intermolecular π–π stacking interactions are beneficial to promote the performance of LIBs.
