Co-reporter:Bin Guo;Lin Ye;Gangfeng Tang;Li Zhang;Bin Yue;Shik Chi Edman Tsang;Heyong He
Chinese Journal of Chemistry 2017 Volume 35(Issue 10) pp:1529-1539
Publication Date(Web):2017/10/01
DOI:10.1002/cjoc.201700084
A series of mesoporous Nb and Nb-W oxides were employed as highly active solid acid catalysts for the conversion of glucose to 5-hydroxymethylfurfural (HMF). The results of solid state 31P MAS NMR spectroscopy with adsorbed trimethylphosphine as probe molecule show that the addition of W in niobium oxide increases the number of Brønsted acid sites and decreases the number of Lewis acid sites. The catalytic performance for Nb-W oxides varied with the ratio of Brønsted to Lewis acid sites and high glucose conversion was observed over Nb5W5 and Nb7W3 oxides with high ratios of Brønsted to Lewis acid sites. All Nb-W oxides show a relatively high selectivity of HMF, whereas no HMF forms over sulfuric acid due to its pure Brønsted acidity. The results indicate fast isomerization of glucose to fructose over Lewis acid sites followed by dehydration of fructose to HMF over Brønsted acid sites. Moreover, comparing to the reaction occurred in aqueous media, the 2-butanol/H2O system enhances the HMF selectivity and stabilizes the activity of the catalysts which gives the highest HMF selectivity of 52% over Nb7W3 oxide. The 2-butanol/H2O catalytic system can also be employed in conversion of sucrose, achieving HMF selectivity of 46% over Nb5W5 oxide.
Co-reporter:Bin Guo;Lin Ye;Gangfeng Tang;Li Zhang;Bin Yue;Shik Chi Edman Tsang;Heyong He
Chinese Journal of Chemistry 2017 Volume 35(Issue 10) pp:1480-1480
Publication Date(Web):2017/10/01
DOI:10.1002/cjoc.201770102
The inside cover picture shows the excellent catalytic performance of mesoporous Nb and Nb-W oxides catalysts for the conversion of glucose to 5-hydroxymethylfurfural. The catalytic activity and selectivity for all Nb-W oxides vary according to the ratio of Brønsted to Lewis acid sites. The highest HMF selectivity of 52% was achieved over Nb7W3 oxide catalyst. More details are discussed in the article by He et al. on page 1529–1539.
Co-reporter:Jie Li, Yuanhang Ren, Bin Yue, Heyong He
Chinese Journal of Catalysis 2017 Volume 38, Issue 7(Volume 38, Issue 7) pp:
Publication Date(Web):1 July 2017
DOI:10.1016/S1872-2067(17)62844-4
Ni/Al2O3 catalysts were derived from spinel NiAl2O4 with different Ni content ((2.5, 5 and 7.5) wt%). The catalysts were obtained by H2 reduction and were investigated for the low-temperature hydrogenation of maleic anhydride (MA) to produce succinic anhydride (SA). The characterization results showed that Ni0 active sites were mainly derived during the H2 reduction from spinel NiAl2O4. Among the catalysts studied, employing the optimum preparation and reaction conditions with Ni(5%)/Al2O3 yielded the highest catalytic performance. A near-100% conversion of MA and ∼90% selectivity to SA were achieved at 120 °C and 0.5 MPa of H2 with a weighted hourly space velocity (MA) of 2 h−1.Ni/Al2O3 catalyst derived from spinel NiAl2O4 shows high performance in low-temperature hydrogenation of maleic anhydride to produce succinic anhydride. 90% yield of succinic anhydride was obtained over Ni/Al2O3 catalyst at 120 °C.Download high-res image (100KB)Download full-size image
Co-reporter:Liya Hu, Cheng Wang, Bin Yue, Xueying Chen, Heyong He
Materials Today Communications 2017 Volume 11(Volume 11) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.mtcomm.2017.02.005
Highly ordered mesoporous carbon of body-centered cubic structure was synthesized by the evaporation induced self-assembly method using Pluronic F127 and phenolic resol as the template and carbon source, respectively. Vanadium species were introduced to the carbon support by both co-assembly and impregnation strategies for comparison. Ordered mesoporous carbon nanoparticles of the same body-centered cubic structure were also synthesized via a facile soft-template method, followed by the incorporation of vanadium species via impregnation. The obtained three different series of vanadium-containing carbon catalysts were tested in the direct benzene hydroxylation reaction using H2O2 as an oxidant. The vanadium supporting mesoporous carbon nanoparticles, due to the open framework and short channels for fast reactants diffusion and the easily accessible active vanadium species for reactants activation, exhibited superior catalytic activity to other series of catalysts. Particularly, the 4V/MCN-S catalyst showed the best catalytic performance among the studied catalysts with a benzene conversion of 38.2% and phenol selectivity of 96.1%, along with good stability during five recycles.Download high-res image (140KB)Download full-size image
Co-reporter:Na Su, Xueying Chen, Bin Yue and Heyong He
Nanoscale 2016 vol. 8(Issue 16) pp:8673-8680
Publication Date(Web):06 Apr 2016
DOI:10.1039/C6NR00771F
A clear understanding of the growth mechanism involved in the shape-controlled synthesis of noble-metal nanocrystals with concave surfaces can provide useful information for the rational design of novel anisotropic nanostructures with controllable properties. In this paper, we conducted a systematic study of the detailed growth mechanism of the Pd arrow-headed tripods and revealed how the formation of the concave Pd nanocrystals was collectively controlled by the reduction kinetics, concentration gradient of Pd precursors, and surface diffusion of atoms. The formation of the arrow-headed tripods can be attributed to an auto-catalytic tip overgrowth process, where the Pd triangular nanoplate seeds formed under a suitably slow reduction rate can auto-catalyze the dehydrogenation of benzyl alcohol to generate hydrogen atoms [H]. The presence of [H] further dramatically accelerates the reduction of Pd(acac)2, which introduces a concentration gradient of Pd precursors in our non-stirring synthesis system and facilitates the kinetically-controlled tip overgrowth under a concentration gradient to form tripods with troughs on the arms. The final shapes of the concave nanocrystals depend on the relative rate of atom deposition and surface diffusion of atoms, which can be tuned by manipulating the reaction conditions such as the reaction temperature and the stirring conditions. This study presents a new possibility for the rational synthesis of various Pd nanostructures by manipulating the auto-catalytic process and tuning the relative rate of atom deposition and surface diffusion of atoms, which provides useful information for understanding the growth mechanism and the design of other anisotropic noble-metal nanostructures.
Co-reporter:Jie Li, Lin-Ping Qian, Li-Ya Hu, Bin Yue, He-Yong He
Chinese Chemical Letters 2016 Volume 27(Issue 7) pp:1004-1008
Publication Date(Web):July 2016
DOI:10.1016/j.cclet.2016.03.021
The pseudo-boehmite derived alumina supported metal (Cu, Co and Ni) catalysts prepared by the impregnation method were investigated in hydrogenation of maleic anhydride (MA) to succinic anhydride (SA) and γ-butyrolactone. The catalysts were characterized by ICP-AES, N2 adsorption–desorption, XRD, H2-TPR, CO-TPD, dissociative N2O adsorption and TEM and the results showed that the alumina possessed mesoporous feature and the metal species were well dispersed on the support. Compared to Cu/Al2O3 and Co/Al2O3, Ni/Al2O3 exhibited higher catalytic activity in the MA hydrogenation with 92% selectivity to SA and nearly 100% conversion of MA at 140 °C under 0.5 MPa of H2 with a weighted hourly space velocity of 2 h−1 (MA). The stability of Ni/Al2O3 catalyst was also investigated.Al2O3 supported Cu, Co and Ni catalysts with high dispersion were obtained by the impregnation method. Ni/Al2O3 showed the highest catalytic performance with ∼100% MA conversion at 140 °C and 0.5 MPa of H2.
Co-reporter:Yichen Hu, Bin Guo, Yingyi Fu, Yuanhang Ren, Gangfeng Tang, Xueying Chen, Bin Yue and Heyong He
Chemical Communications 2015 vol. 51(Issue 75) pp:14219-14222
Publication Date(Web):10 Aug 2015
DOI:10.1039/C5CC04548G
Sulfated titania solid superacids with dominant {001}, {001}/{101}, and {101} facets were prepared by the hydrothermal method and subsequent sulfation. Their facet-dependent acidic properties were investigated by the solid-state 31P NMR technique and Pechmann condensation of 5,7-dihydroxy-4-methyl coumarin.
Co-reporter:Na Su, Xueying Chen, Yuanhang Ren, Bin Yue, Han Wang, Wenbin Cai and Heyong He
Chemical Communications 2015 vol. 51(Issue 33) pp:7195-7198
Publication Date(Web):26 Mar 2015
DOI:10.1039/C5CC00353A
Single crystalline palladium arrow-headed tripods prepared via a simple one-pot strategy exhibit high electro-activity in formic acid oxidation, which could be a promising anodic catalyst for direct formic acid fuel cells.
Co-reporter:Na Su, Xueying Chen, Bin Yue and Heyong He
Catalysis Science & Technology 2015 vol. 5(Issue 2) pp:638-649
Publication Date(Web):27 Oct 2014
DOI:10.1039/C4CY00871E
This review mainly summarizes our latest progress in the preparation of free-standing mesoporous metal catalysts and their applications in heterogeneous enantioselective hydrogenations. Owing to exclusion of the support effect, free-standing mesoporous metal could be a suitable experimental model for a mechanistic understanding, which would have significant benefits for the design of real catalysts with high performance. We start with a brief survey on the main synthetic approaches available for the preparation of free-standing mesoporous metal catalysts. Next, we select a few mesoporous metal catalysts to demonstrate their improved catalytic performance in the enantioselective hydrogenation of ketones or aromatic ketones. The factors influencing the activity and enantioselectivity, such as the modification conditions and confinement effect, are discussed. Finally, we introduce DFT calculations to gain insight into the molecular interaction involved in the adsorption process. We conclude the review with a personal perspective on the challenges and opportunities for the future development of efficient heterogeneous enantioselective metal catalysts.
Co-reporter:Min Gu;Yuanhang Ren;Yichen Hu;Min Tang;Zuping Kong;Bin Yue;Heyong He
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 3) pp:488-493
Publication Date(Web):
DOI:10.1002/ejic.201402938
Abstract
The reactions of silicotungstate, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo), and copper, cobalt, or nickel acetate under hydrothermal condition yield the three compounds [(SiW12O40)Cu2(3-bpo)2(C5H4NCOOH)2]·H2O (1), [(SiW12O40)Co2(3-bpo)2(C5H4NCOOH)2(H2O)2]·2H2O (2), and [(SiW12O40)Ni2(3-bpo)2(C5H4NCOOH)2(H2O)2]·3H2O (3), respectively, in which the nicotinic acid ligands are generated from the in situ decomposition of 3-bpo during the hydrothermal process. In the three structures, the polyoxometalate (POM) serves as the center and is imbedded within the dimetallic cyclic [M2(3-bpo)2(C5H4NCOOH)2]4+ moiety through coordination bonds to form infinite one-dimensional (1D) supramolecular snadwich-like structures. Owing to the difference in the metal ions, the packing style of [Cu2(3-bpo)2(C5H4NCOOH)2]4+ is different from that of [M2(3-bpo)2(C5H4NCOOH)2]4+ (M = Co, Ni). The electrochemical behaviors of compounds 1–3 were studied by cyclic voltammetry.
Co-reporter:Yingyi Fu;Yanan Wu;Wenjia Cai;Bin Yue;Heyong He
Science China Chemistry 2015 Volume 58( Issue 1) pp:148-155
Publication Date(Web):2015 January
DOI:10.1007/s11426-014-5251-3
A series of Ce-promoted 6.7% Ni-containing mesoporous silica (Ce-Ni-SiO2) with varying Ce content (0.5%–4.8%) was prepared using the evaporation-induced self-assembly method. The characterization results showed that Ce and Ni species were homogeneously incorporated into the mesoporous silica matrix. The catalytic properties of these samples in the dry reforming of methane reaction revealed that the catalysts (e.g., 1.2% Ce-Ni-SiO2) containing highly dispersed small Ni particles exhibited excellent catalytic activity and long-term stability, which is attributed to the anchoring effect of the Ce and its ability to increase surface oxygen species concentration.
Co-reporter:Wen-Jia Cai, Lin-Ping Qian, Bin Yue, He-Yong He
Chinese Chemical Letters 2014 Volume 25(Issue 11) pp:1411-1415
Publication Date(Web):November 2014
DOI:10.1016/j.cclet.2014.06.016
A series of SBA-15 supported bimetallic Rh–Ni catalysts with different weight ratio of Rh/Ni in the range of 0–0.04 were prepared for carbon dioxide reforming of methane. The doping effect of Rh on catalytic activity as well as carbon accumulation and removal over the catalysts was studied. The characterization results indicated that the addition of a small amount of Rh promoted the reducibility of Ni particles and decreased the Ni particle size. During the dry reforming reaction, the carbon deposition was originated from CH4 decomposition and CO disproportionation. The Rh–Ni catalyst with small metallic particle size inhibited the carbon formation and exhibited high efficiency in the removal of coke. In comparison with bare Ni-based catalyst, the Rh–Ni bimetallic catalysts showed high activity and stability in the dry reforming of methane.In comparison with bare Ni-based catalyst, the Rh–Ni catalyst with smaller Ni particle size exhibited high efficiency in the removal of coke and showed high activity and stability in the dry reforming of methane.
Co-reporter:Zuping Kong;Bin Yue;Wei Deng;Kake Zhu;Mengguo Yan;Yangfeng Peng;Heyong He
Applied Organometallic Chemistry 2014 Volume 28( Issue 4) pp:239-243
Publication Date(Web):
DOI:10.1002/aoc.3115
Synthesis of hierarchically porous zeolites has drawn intensive interest because of their improved catalytic performance. It is highly desirable to find ways to generate these materials in a low-cost and scalable way for their commercial applications. A solvent evaporation route has been established to synthesize hierarchically porous titanosilicalite-1 (TS-1). In the protocol, hexadecyltrimethoxysilane was added to an ethanolic solution of titanium isopropoxide, tetraethyl orthosilicate and tetrapropylammonium hydroxide, i.e. the embryo solution of TS-1. The solution was subjected to solvent evaporation-induced self-assembly to afford an ordered dry gel. Subsequent steam-assisted crystallization converted the dry gel into a hierarchically porous TS-1. X-ray powder diffraction (XRD), UV–visible diffusive reflectance spectroscopy, N2 physisorption and electron microscopic characterizations have been employed to elucidate the structure. Ti is incorporated into the tetrahedral sites of the MFI structure and mesopores around 20 nm penetrating the crystalline framework are formed. Hexadecyltrimethoxysilane plays a key role in creating mesopores as well as increasing the crystal size. The hierarchically porous TS-1 exhibits improved activity in styrene oxidation and phenol hydroxylation. Copyright © 2014 John Wiley & Sons, Ltd.
Co-reporter:Yichen Hu;Yuanhang Ren;Gangfeng Tang;Cheng Wang;Min Tang;Bin Yue;Heyong He
Chinese Journal of Chemistry 2014 Volume 32( Issue 11) pp:1151-1156
Publication Date(Web):
DOI:10.1002/cjoc.201400383
Abstract
TiO2 nanosheets with dominant {001} facets, coupled with Cs2.5H0.5PW12O40, were successfully synthesized by a one-step hydrothermal reaction. The photocatalytic activity of nanocatalysts was evaluated by the degradation of Rhodamine B under UV light irradiation. The results showed that both the addition of Cs2.5H0.5PW12O40 and the exposed {001} facets of TiO2 have a positive effect on the photocatalytic activity. The improved photoactivity of nanocomposites in comparison with that of TiO2 nanosheets could be attributed to the synergistic effect between Cs2.5H0.5PW12O40 and TiO2 which facilitates the separation of photo-induced hole-electron pairs.
Co-reporter:Yuanhang Ren, Yichen Hu, Yucheng Shan, Zuping Kong, Min Gu, Bin Yue, Heyong He
Inorganic Chemistry Communications 2014 40() pp: 108-111
Publication Date(Web):
DOI:10.1016/j.inoche.2013.11.037
Co-reporter:Li Zhang, Bin Yue, Yuanhang Ren, Xueying Chen and Heyong He
Catalysis Science & Technology 2013 vol. 3(Issue 8) pp:2113-2118
Publication Date(Web):02 May 2013
DOI:10.1039/C3CY00121K
Aluminum doped cesium salts of tungstophosphoric acid, AlxCs2.5–3xH0.5PW12O40 (x = 0.05, 0.1 and 0.15), were prepared via a solid state synthesis method and their catalytic activity in n-butane isomerization reaction was tested using the 13C MAS NMR technique and 1-13C-n-butane as the reactant. All AlxCs2.5–3xH0.5PW12O40 catalysts show higher catalytic activity than Cs2.5H0.5PW12O40. Among them, Al0.1Cs2.2H0.5PW12O40 exhibits the best performance. The MAS NMR technique was further employed to characterize the acidity of the catalysts using trimethylphosphine and 2-13C-acetone as the basic probe molecules. Al0.1Cs2.2H0.5PW12O40 possesses higher Brönsted acid strength than Cs2.5H0.5PW12O40, which parallels the activity of the catalysts. For a catalyst used in n-butane isomerization reaction, to enhance its Brönsted acid strength rather than to increase its acid density is more important for improving the activity of the catalyst.
Co-reporter:Mingli Deng, Xiaofeng Liu, Qingshu Zheng, Zhenxia Chen, Changye Fang, Bin Yue and Heyong He
CrystEngComm 2013 vol. 15(Issue 35) pp:7056-7061
Publication Date(Web):08 Jul 2013
DOI:10.1039/C3CE40673C
3-Phosphonobenzoic acid (3-H3pbc) was designed as an extended 4-connected ligand to build zeolite-like metal–organic frameworks (ZMOFs). Controlled assembly of Zn2+ with ligand 3-H3pbc results in two distinct structures with zeolitic topologies of MER and RHO, namely [Zn(3-pbc)]·H3O·0.5H2O (1) and Zn2.5(3-pbc)2(H2O)·nS (S represents the disordered solvent molecules) (2), respectively. The framework of 1 consists of double crankshaft chains formed by alternating ZnO4 and O3PC tetrahedra that are cross-linked by 3-pbc to generate a three-dimensional zeolitic open-framework. It is worth noting that structure 2 builds a zeolitic framework in a novel way, which has not been found in other metal phosphonocarboxylates. The organic part of 3-pbc does not participate in the construction of zeolitic topology and only plays a decorative role inside the cages.
Co-reporter:Wen-Jia Cai, Lin-Ping Qian, Bin Yue, Xue-Ying Chen, He-Yong He
Chinese Chemical Letters 2013 Volume 24(Issue 9) pp:777-779
Publication Date(Web):September 2013
DOI:10.1016/j.cclet.2013.05.034
A series of Co/Mg–Al oxide samples, CoMgAl-x (x = (Mg + Co)/Al molar ratio of 1–5), were prepared by the self-combustion method followed by H2 reduction. The catalytic performance and stability of the samples were studied in dry reforming of CH4. XRD and H2-TPR characterization results showed that the reduced CoMgAl-x samples mainly consisted of solid solution and spinel phases with cobalt particles. The spinel phases contained Co3O4 and ConMg1-nAl2O4 (0 ≤ n ≤ 1) varying with the (Mg + Co)/Al ratio. The effect of (Mg + Co)/Al molar ratio on the catalytic behavior was investigated in detail and CoMgAl-3 exhibited the highest catalytic activity and stability among the catalysts studied.Co/Mg–Al oxide catalysts (CoMgAl-x, x = 1–5), particularly CoMgAl-3, prepared by the self-combustion method show high catalytic activity and stability in the methane dry reforming reaction.
Co-reporter:Li Zhang, Yuanhang Ren, Bin Yue and Heyong He
Chemical Communications 2012 vol. 48(Issue 18) pp:2370-2384
Publication Date(Web):03 Jan 2012
DOI:10.1039/C2CC16882K
In situ NMR studies of C1–C5 light alkane activation and functionalisation in heterogeneous catalytic systems are overviewed. The results obtained from the NMR technique, particularly those quantitative ones, provide unique information on the activation of alkane molecules and the nature of relevant intermediates, leading to better understanding reaction mechanisms and designing catalysts.
Co-reporter:Zuping Kong;Chunling Wang;Yuanhang Ren;Min Gu;Yichen Hu;Bin Yue;Heyong He
Chinese Journal of Chemistry 2012 Volume 30( Issue 4) pp:759-764
Publication Date(Web):
DOI:10.1002/cjoc.201100439
Abstract
Two compounds, namely [Cd(HINA)2(µ2-H2O)(H2O)2]2[SiW12O40]·6H2O (1) and [Co(HINA)3(H2O)3][Co(HINA)2(H2O)4][SiW12O40]·2H2O (2), have been synthesized from the aqueous mixture containing H4SiW12O40, isonicotinic acid (HINA), and M(CH3COO)2 (M=Cd and Co). The compounds have been characterized by elemental analysis, IR spectroscopy, TG analysis, and single-crystal X-ray diffraction. The dinuclear coordinated cadmium units in compound 1 are linked to form 2D layer parallel to ab plane through π-π interactions and hydrogen bonds. Compound 2 contains two different types of coordinated metal cations, [Co(HINA)3(H2O)3]2+ and [Co(HINA)2(H2O)4]2+, which construct 2D layer along bc plane through π-π interactions and hydrogen bonds. In both compounds, the Keggin anions are located inside the channels and cavities formed from stack of the coordinated metal cations, which further achieve the 3D supramolecular structure through hydrogen bonds. The luminescent property of compounds 1 and 2 has been investigated.
Co-reporter:Yu Wang;Xueying Chen;Bin Yue;Heyong He
Topics in Catalysis 2012 Volume 55( Issue 14-15) pp:1022-1031
Publication Date(Web):2012 October
DOI:10.1007/s11244-012-9884-1
Mesoporous Ni–P amorphous alloy nanospheres with controllable sizes and compositions were synthesized by chemical reduction of Ni(OH)2 colloidal particles co-assembling with surfactant hexadecyl-trimethyl-ammonium bromide in liquid crystal mesophase using hypophosphite as reductant. The effects of the synthesis conditions on the particle size, composition and mesostructure of the mesoporous Ni–P nanospheres were systematically studied. It was found that the size of the mesoporous Ni–P nanospheres could be tuned from 35 to 90 nm by changing the reduction temperature, and the phosphorus content of the Ni–P products could be adjusted in the range of 20.1 to 27.6 % by changing the molar ratio of H2PO2−/Ni2+. The active surface area and the thermal stability of the mesoporous Ni–P nanosphere catalyst are much higher than those for the conventional nonporous Ni–P amorphous alloy. In the liquid phase hydrogenation of nitrobenzene, the typical mesoporous Ni–P nanosphere catalyst exhibits much higher activity and better selectivity than the conventional nonporous Ni–P. The correlation between the catalytic performance and the structural properties is discussed based on the results of detailed characterization.
Co-reporter:Lin Ye, Yu Wang, Xueying Chen, Bin Yue, Shik Chi Tsang and Heyong He
Chemical Communications 2011 vol. 47(Issue 26) pp:7389-7391
Publication Date(Web):31 May 2011
DOI:10.1039/C1CC11652E
Three-dimensionally ordered mesoporous Pd networks fabricated by a simple reduction method in solution using a face centered cubic silica super crystal as template exhibit high electroactivity in formic acid oxidation.
Co-reporter:Yuanhang Ren, Chengbo Du, Sujiao Feng, Chunling Wang, Zuping Kong, Bin Yue and Heyong He
CrystEngComm 2011 vol. 13(Issue 23) pp:7143-7148
Publication Date(Web):21 Sep 2011
DOI:10.1039/C1CE06037F
Three polyoxometalates (POM)-based coordination polymers, [CuII2(C5H5NCOO)2(4-bpo)2(H2O)2]SiW12O40·H2O (1), [CuI4(4-bpo)6]SiW12O40·3H2O (2), and [CuI4(3-bpo)4]SiW12O40·3H2O (3), were hydrothermally synthesized from the mixture of H4SiW12O40, copper salts, and 3-bpo (2,5-bis(3-pyridyl)-1,3,4-oxadiazole) or 4-bpo (2,5-bis(4-pyridyl)-1,3,4-oxadiazole) and characterized by elemental analysis, IR spectroscopy, TG analysis, and single crystal X-ray diffraction. The 4-bpo molecules are connected into an infinite double-chain in compound 1 as a bidentate ligand. Compound 2 contains large hexagonal prism shaped molecular cages defined by copper ions and 4-bpo molecules which wrap Keggin ions inside. In compound 3 {Cu2(3-bpo)2} molecular rings connect with Keggin ions to form a 1D chain. By inspection of the structures, the geometry and the coordination mode of bpo ligands play important roles in the formation of 1–3. The catalytic performance of 1–3 was investigated for epoxidation of styrene using tert-butyl hydroperoxide (TBHP) as the oxidant. Compounds 1–3 present promising activity as heterogeneous catalysts while compound 1 exhibits the best yield of styrene epoxide.
Co-reporter:Mingli Deng;Dr. Yun Ling;Bing Xia;Dr. Zhenxia Chen;Dr. Yaming Zhou;Xiaofeng Liu;Dr. Bin Yue ;Dr. Heyong He
Chemistry - A European Journal 2011 Volume 17( Issue 37) pp:10323-10328
Publication Date(Web):
DOI:10.1002/chem.201101239
Abstract
Three isoreticular zinc(II)-phosphonocarboxylate frameworks, namely {[Zn3(pbdc)2]⋅2 H3O}n (ZnPC-2), {[Zn3(pbdc)2]⋅Hpd⋅H3O⋅4 H2O}n (Hpd@ZnPC-2) and {[Co1.5Zn1.5(pbdc)2]⋅2 H3O}n (CoZnPC-2) (H4pbdc=5-phosphonobenzene-1,3-dicarboxylic acid, pd=pyrrolidine), were solvothermally synthesized. ZnPC-2 has a 3D structure based on trinuclear ZnII clusters (Zn3-SBU) showing 3D interconnected channels. Hpd@ZnPC-2 contains an isoreticular framework of ZnPC-2 with small channels blocked by Hpd molecules. In CoZnPC-2, ZnII ions in ZnPC-2 are partially substituted by CoII ions. The Friedel–Crafts benzylation reactions were carried out over these isoreticular porous materials. The catalytic results reveal that ZnPC-2 is an excellent heterogeneous Lewis acid catalyst with a high selectivity (>90 %) towards less bulky para-oriented products. The catalytic reaction has been proved to occur inside the pore of ZnPC-2, and the immobilized Zn3-SBUs are the active sites.
Co-reporter:Lin Ye, Songhai Xie, Bin Yue, Linping Qian, Sujiao Feng, Shik Chi Tsang, Yingcheng Li and Heyong He
CrystEngComm 2010 vol. 12(Issue 2) pp:344-347
Publication Date(Web):25 Sep 2009
DOI:10.1039/B913268F
A well-ordered three-dimensional (3D) cubic Ia3d mesoporous niobium oxide with amorphous wall is prepared under controlled humidity by a sol-gel method and further converted to crystalline 3D niobium oxide with the retention of its original mesoporous system.
Co-reporter:Chunling Wang, Yuanhang Ren, Chengbo Du, Bin Yue, Zuping Kong, Linhong Weng and Heyong He
CrystEngComm 2010 vol. 12(Issue 11) pp:3522-3525
Publication Date(Web):26 Jul 2010
DOI:10.1039/C004543H
A honeycomb nanoscale-porous material constructed from straight metal–organic chains and octahedral Lindqvist-type polyoxoanion building blocks is solvothermally synthesized, exhibiting a hexagonal array of one-dimensional pores similar with that of MCM-41. The pore sizes are in the range of 16.33 to 23.71 Å and the sorption property of the material is investigated.
Co-reporter:Linping Qian; Dr. Bin Yue;Supeng Pei;Li Zhang;Lin Ye;Jifang Cheng;Shik Chi Tsang; Dr. Heyong He
Chinese Journal of Chemistry 2010 Volume 28( Issue 10) pp:1864-1870
Publication Date(Web):
DOI:10.1002/cjoc.201090311
Abstract
The effect of Rh dispersion on reforming of CH4 with CO2 over H-Beta supported Rh catalysts has been investigated. The CH4 and CO2 conversion over the catalysts increase with increasing Rh loading from 0.5 wt% to 4.0 wt% in the reaction temperature range of 823–1123 K. The high TOF of CH4 over 0.5 wt% and 1.0 wt% Rh/H-beta may be attributed to high dispersion of rhodium species. The catalysts before and after the reaction were characterized by XRD, TEM, and TG-DTA and the results indicate the catalysts with Rh loading of 0.5 wt% and 1.0 wt% exhibiting high resistance to coke. Under controllable conditions, we confirm that the coke is originated from methane dissociation and can be substantially oxidized by active oxygen species dissociated from the adsorbed carbon dioxide on the catalyst with high dispersion of Rh species.
Co-reporter:Zhiying Lou, Xueying Chen, Li Tian, Minghua Qiao, Kangnian Fan, Heyong He, Xiaoxin Zhang, Baoning Zong
Journal of Molecular Catalysis A: Chemical 2010 326(1–2) pp: 113-120
Publication Date(Web):
DOI:10.1016/j.molcata.2010.04.018
Co-reporter:Chun Xia He, Bin Yue, Ji Fang Cheng, Wei Ming Hua, Ying Hong Yue, He Yong He
Chinese Chemical Letters 2009 Volume 20(Issue 7) pp:869-872
Publication Date(Web):July 2009
DOI:10.1016/j.cclet.2009.02.021
Mesoporous tetragonal sulfated zirconia with high surface area and narrow pore-size distribution was prepared using Zr(O-nPr)4 as zirconium precursor, sulfuric acid as sulfur source and triblock copolymer poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) (P123) as the template. The samples were characterized by X-ray diffraction, N2 sorption, TEM, and NH3-TPD. A phase transformation from monoclinic sulfated zirconia to tetragonal sulfated zirconia is observed. The product shows strong acidity.
Co-reporter:Min Gu, Bin Yue, Renlie Bao, Heyong He
Materials Research Bulletin 2009 44(6) pp: 1422-1427
Publication Date(Web):
DOI:10.1016/j.materresbull.2008.11.018
Co-reporter:Jifang Cheng, Supeng Pei, Bin Yue, Linping Qian, Chunxia He, Yan Zhou, Heyong He
Microporous and Mesoporous Materials 2008 Volume 115(Issue 3) pp:383-388
Publication Date(Web):1 November 2008
DOI:10.1016/j.micromeso.2008.02.009
Hollow microspheres of ZSM-5 with a mesoporous shell have been synthesized through formation of amorphous hollow SiO2/Al2O3 microspheres by sol–gel process in multiple oil–water–oil emulsions and transformation of the amorphous species into zeolite by water–organic vapor-phase transport treatment at 160 °C for 8 days. The morphology of the amorphous and zeolite spheres observed by scanning electron microscopy shows no significant change whereas the molar ratio of Si/Al increases from 6 to 20 during the transformation. The structural feature of zeolite was characterized by X-ray diffraction and 29Si and 27Al magic-angle spinning nuclear magnetic resonance. Transmission electron microscopy and N2 adsorption–desorption isotherms indicate that uniform mesopores in the shell of zeolite spheres arise from the interstices among zeolite crystallites.
Co-reporter:Supeng Pei, Bin Zhang, Kun Jiao, Renlie Bao, Bin Yue, Heyong He
Acta Physico-Chimica Sinica 2008 Volume 24(Issue 4) pp:561-564
Publication Date(Web):April 2008
DOI:10.1016/S1872-1508(08)60022-4
Nanostructured cobalt molybdate catalysts supported on mesoporous silica SBA-15 with different loadings were prepared by citric acid coordination-impregnation method and characterized by XRD, TEM, and BET techniques. The characterization results showed that high loading of well-dispersed crystalline CoMoO4 may be achieved using citric acid coordination-impregnation method and the mesoporous structure of the support remained intact. The catalytic activity of these catalysts in the oxidative dehydrogenation of propane was investigated. The catalysts of nanostructured cobalt molybdate supported on mesoporous silica SBA-15 showed better catalytic performance than the corresponding bulk composite oxide and nanostructured CoMoO4 supported on SBA-15 with loading of 13% (mass fraction, w) displayed propene yield of 16.8% at 823 K.
Co-reporter:Shixi Liu, Bin Yue, Kun Jiao, Yan Zhou, Heyong He
Materials Letters 2006 Volume 60(Issue 2) pp:154-158
Publication Date(Web):January 2006
DOI:10.1016/j.matlet.2005.08.008
Zinc and iron nitrates with molar ratio of 1 : 2 were introduced into mesoporous silica host SBA-15 via a “two-solvent” route. The thermal decomposition of the precursors inside SBA-15 and the formation of spinel phase were monitored by X-ray diffraction, thermogravimetric and differential thermal analysis. The one-dimensional nanostructured spinel zinc ferrite in mesopores and pure spinel ZnFe2O4 nanowires, obtained through complete removal of the silica template with aqueous NaOH solution, were confirmed by TEM. The nanowires exhibited superparamagnetism at room temperature, whereas the bulk spinel ZnFe2O4 showed weak paramagnetism.
Co-reporter:Ai-Jie Han Dr.;Juan Guo;Hui Yu Dr.;Yu Zeng Dr.;Yue-Fang Huang ;He-Yong He
ChemPhysChem 2006 Volume 7(Issue 3) pp:607-613
Publication Date(Web):3 FEB 2006
DOI:10.1002/cphc.200500389
Affinity index (AT value), adsorption heat, X-ray diffraction (XRD), and 13C and 29Si magic-angle spinning (MAS) NMR, FTIR, and Raman spectroscopies were used to study the interaction of highly siliceous MFI-, FAU-, and FER-type zeolites with adsorbed methylamine (MA). Compared with the data for methanol, the much higher AT values and adsorption heats, and significant changes in XRD patterns, 29Si MAS NMR spectra, and FTIR spectra for the zeolites after adsorption of MA, revealed a strong hydrogen-bonding interaction between the perfect framework of the zeolites and the adsorbed MAs. This interaction results from the fact that the H atom of the amine group attacks the [SiO] framework to form a SiO⋅⋅⋅H⋅⋅⋅N bond, which leads to the appearance of SiN bonds in the zeolites at 323 K. Therefore, the zeolite framework can be modified with MA under mild conditions. The highly siliceous MFI zeolite and the H-ZSM-5 zeolite with SiO2 /Al2O3=31:1 were modified with MA and investigated by temperature-programmed desorption of CO2. The modified zeolites exhibited greatly enhanced basic properties in comparison with those of the raw materials. The influence of defects in the zeolite on the adsorption and the interaction with MA is discussed.
Co-reporter:Kun Jiao, Bin Zhang, Bin Yue, Yu Ren, Shixi Liu, Shirun Yan, Calum Dickinson, Wuzong Zhou and Heyong He
Chemical Communications 2005 (Issue 45) pp:5618-5620
Publication Date(Web):20 Oct 2005
DOI:10.1039/B512080B
Single-crystal Cr2O3 with regular mesopores has been synthesized using mesoporous silica KIT-6 as a template and characterized by using XRD, HRTEM and nitrogen adsorption/desorption.
Co-reporter:Bin Yue, Huili Tang, Zuping Kong, Kake Zhu, Calum Dickinson, Wuzong Zhou, Heyong He
Chemical Physics Letters 2005 Volume 407(1–3) pp:83-86
Publication Date(Web):17 May 2005
DOI:10.1016/j.cplett.2005.03.066
Abstract
Three-dimensional (3D) mesoporous tungsten oxide single crystals has been prepared by using aminosilylized 3D mesoporous SBA-15 as the template and characterized by X-ray diffraction, transmission electron microscopy, and selected area electron diffraction. The product is an array of hexagonally ordered nanorods linked by nanosized bridges to form a 3D open framework as an inverse replica of SBA-15.
Co-reporter:Bin Yue;De-Jun Tan;Shi-Run Yan;Yan Zhou;Ka-Ke Zhu;Jian-Feng Pan;Ji-Hua Zhuang;He-Yong He
Chinese Journal of Chemistry 2005 Volume 23(Issue 1) pp:32-36
Publication Date(Web):26 JAN 2005
DOI:10.1002/cjoc.200590008
A new approach was developed to fabricate nanowires of mixed oxides MoO3-V2O5 inside the channels of mesoporous silica SBA-15. The method involves functionalization of the channel surface of SBA-15 with aminosilane groups, immobilization of Keggin-type molybdovanadophosphoric acids through an acid-base interaction, and heat treatment. The immobilization of the heteropolyacid containing mixed addenda makes the molar ratio of the loaded components controllable. The formation of the MoO3-V2O5 nanowires inside the channels was monitored by variable temperature in situ XRD. The materials obtained by heat treatment at 400 °C for 5 h were characterized by TEM, N2-sorption measurements, laser Raman spectra and UV-Vis diffuse reflectance spectra. Further heat treatment of the MoO3-V2O5 nanowires inside the SBA-15 channels at higher temperature (700 °C) destroys the framework integrity of SBA-15 by complete sublimation of MoO3 through the SBA-15 channel walls.
Co-reporter:Yingcheng Li, Shirun Yan, Weimin Yang, Zaiku Xie, Qingling Chen, Bin Yue, Heyong He
Journal of Molecular Catalysis A: Chemical 2005 Volume 226(Issue 2) pp:285-290
Publication Date(Web):15 February 2005
DOI:10.1016/j.molcata.2004.10.047
Effect of MgAl2O4 on the structure, acidity as well as the catalytic performance of Nb2O5/α-Al2O3 catalyst for ethylene oxide hydration was studied using IR, XRD, NH3-TPD, CO2-TPD and catalytic reaction. Modification of α-Al2O3 support with MgAl2O4 led to an increase in both basicity and mechanical strength of the support. As a result, the density and strength of the acidity of the niobium oxide catalyst supported on the MgAl2O4 modified α-Al2O3 reduced in comparison with that supported on the pure α-Al2O3. The acidity of 10% Nb2O5/MgAl2O4/α-Al2O3 decreased with increasing loading of MgAl2O4. Catalytic test showed that EO conversion decreased monotonously with increasing MgAl2O4 loading, whereas the selectivity to MEG exhibited a maximum of 90.6% at MgAl2O4 loading of 2.23%. In terms of MEG yield, optimal MgAl2O4 loading should be around 2%. Durability test demonstrated that 10% Nb2O5/MgAl2O4/α-Al2O3 catalyst exhibited excellent stability within 1000 h time-on-stream.Effect of modification of α-Al2O3 support with MgAl2O4 on the structure, acidity as well as the catalytic performance of Nb2O5/α-Al2O3 catalyst for ethylene oxide hydration was studied using IR, XRD, NH3-TPD, CO2-TPD and catalytic reaction.
Co-reporter:Kake Zhu, Bin Yue, Wuzong Zhou and Heyong He
Chemical Communications 2003 (Issue 1) pp:98-99
Publication Date(Web):28 Nov 2002
DOI:10.1039/B210065G
Three-dimensional porous chromium oxide single crystals have been prepared by aminosilylation of the surface silanols of the template, SBA-15, anchoring of dichromic acid to the grafted amine groups, thermal decomposition of inorganic and organic compounds, and removal of the silica framework with HF.
Co-reporter:Kake Zhu, Heyong He, Songhai Xie, Xuan Zhang, Wuzong Zhou, Songlin Jin, Bin Yue
Chemical Physics Letters 2003 Volume 377(3–4) pp:317-321
Publication Date(Web):15 August 2003
DOI:10.1016/S0009-2614(03)01206-5
Abstract
A new method is developed to obtain crystalline nanowires of WO3 using mesoporous silica SBA-15 as template. The method includes aminosilylation of the surface silanols within SBA-15 channels, anchoring of the heteropoly acid (HPA) to the grafted amine groups, thermal decomposition of the HPA, and removal of the silica framework with HF. The formation of the crystalline nanowires is monitored by the in situ XRD technique. TEM images intuitively confirm that the nanowires are uniform in diameter and HRTEM images further indicate that each nanowire belongs to single crystal although the growth orientations of these nanowires are different.
Co-reporter:Kake Zhu, Zhuona Ma, Yan Zou, Wuzong Zhou, Tong Chen and Heyong He
Chemical Communications 2001 (Issue 24) pp:2552-2553
Publication Date(Web):22 Nov 2001
DOI:10.1039/B107487N
Bi-metallic
VOx–SbOx/SBA-15, which may be
used as a site-isolated model catalyst, is successfully prepared by a
two-stage grafting method using a vanadium matallocene and SbCl5
as precursors.
Co-reporter:Yu Wang, Na Su, Lin Ye, Yuanhang Ren, Xueying Chen, Yujue Du, Zhenhua Li, Bin Yue, Shik Chi Edman Tsang, Qiao Chen, Heyong He
Journal of Catalysis (May 2014) Volume 313() pp:113-126
Publication Date(Web):1 May 2014
DOI:10.1016/j.jcat.2014.03.004
•Free-standing mesoporous Pd was used in asymmetric hydrogenation of aromatic ketone.•Enantioselectivity (ee) was effectively tuned by altering the confinement effect.•Confinement effect was optimized by good control of nanoporosity and lattice property.•Optimized Pd catalyst exhibited 40–73% ee at 273 K under atmospheric pressure of H2.•DFT study found ee was linearly correlated with ΔE between prochiral-R & -S complexes.The confinement effect on enantioselective hydrogenation of acetophenone and its derivatives over free-standing mesoporous Pd network catalysts was systematically studied. It was found for the first time that the enantiomeric excess (ee) could be effectively tuned by altering the confinement effect optimized by precise control of the topology, pore size, and lattice structure of mesoporous Pd catalysts. The double gyroid structure with proper pore size and desired lattice structure formed by KBH4 reduction provided suitable microenvironment to generate optimized confinement effect. The optimized catalyst exhibited ee of 40–73% at 273 K under atmospheric pressure of H2. DFT study revealed that the major enantiomeric product could be predicted by comparing relative energies of prochiral-R and -S complexes formed by acetophenone derivatives with S-proline. The energetically favored complex led to the formation of the corresponding enantiomer in excess upon hydrogenation, and ee was found to be linearly correlated with the energy difference between prochiral-R and -S complexes.Download high-res image (293KB)Download full-size image
Co-reporter:Liya Hu, Bin Yue, Cheng Wang, Xueying Chen, Heyong He
Applied Catalysis A: General (5 May 2014) Volume 477() pp:141-146
Publication Date(Web):5 May 2014
DOI:10.1016/j.apcata.2014.03.019
Co-reporter:Linping Qian, Yu Ren, Hui Yu, Yu Wang, Bin Yue, Heyong He
Applied Catalysis A: General (15 July 2011) Volume 401(Issues 1–2) pp:114-118
Publication Date(Web):15 July 2011
DOI:10.1016/j.apcata.2011.05.004
Co-reporter:Supeng Pei, Bin Yue, Linping Qian, Shirun Yan, Jifang Cheng, Yan Zhou, Songhai Xie, Heyong He
Applied Catalysis A: General (1 October 2007) Volume 329() pp:148-155
Publication Date(Web):1 October 2007
DOI:10.1016/j.apcata.2007.07.008
Co-reporter:Li Zhang, Yuanhang Ren, Bin Yue and Heyong He
Chemical Communications 2012 - vol. 48(Issue 18) pp:NaN2384-2384
Publication Date(Web):2012/01/03
DOI:10.1039/C2CC16882K
In situ NMR studies of C1–C5 light alkane activation and functionalisation in heterogeneous catalytic systems are overviewed. The results obtained from the NMR technique, particularly those quantitative ones, provide unique information on the activation of alkane molecules and the nature of relevant intermediates, leading to better understanding reaction mechanisms and designing catalysts.
Co-reporter:Lin Ye, Yu Wang, Xueying Chen, Bin Yue, Shik Chi Tsang and Heyong He
Chemical Communications 2011 - vol. 47(Issue 26) pp:NaN7391-7391
Publication Date(Web):2011/05/31
DOI:10.1039/C1CC11652E
Three-dimensionally ordered mesoporous Pd networks fabricated by a simple reduction method in solution using a face centered cubic silica super crystal as template exhibit high electroactivity in formic acid oxidation.
Co-reporter:Na Su, Xueying Chen, Yuanhang Ren, Bin Yue, Han Wang, Wenbin Cai and Heyong He
Chemical Communications 2015 - vol. 51(Issue 33) pp:NaN7198-7198
Publication Date(Web):2015/03/26
DOI:10.1039/C5CC00353A
Single crystalline palladium arrow-headed tripods prepared via a simple one-pot strategy exhibit high electro-activity in formic acid oxidation, which could be a promising anodic catalyst for direct formic acid fuel cells.
Co-reporter:Li Zhang, Bin Yue, Yuanhang Ren, Xueying Chen and Heyong He
Catalysis Science & Technology (2011-Present) 2013 - vol. 3(Issue 8) pp:NaN2118-2118
Publication Date(Web):2013/05/02
DOI:10.1039/C3CY00121K
Aluminum doped cesium salts of tungstophosphoric acid, AlxCs2.5–3xH0.5PW12O40 (x = 0.05, 0.1 and 0.15), were prepared via a solid state synthesis method and their catalytic activity in n-butane isomerization reaction was tested using the 13C MAS NMR technique and 1-13C-n-butane as the reactant. All AlxCs2.5–3xH0.5PW12O40 catalysts show higher catalytic activity than Cs2.5H0.5PW12O40. Among them, Al0.1Cs2.2H0.5PW12O40 exhibits the best performance. The MAS NMR technique was further employed to characterize the acidity of the catalysts using trimethylphosphine and 2-13C-acetone as the basic probe molecules. Al0.1Cs2.2H0.5PW12O40 possesses higher Brönsted acid strength than Cs2.5H0.5PW12O40, which parallels the activity of the catalysts. For a catalyst used in n-butane isomerization reaction, to enhance its Brönsted acid strength rather than to increase its acid density is more important for improving the activity of the catalyst.
Co-reporter:Na Su, Xueying Chen, Bin Yue and Heyong He
Catalysis Science & Technology (2011-Present) 2015 - vol. 5(Issue 2) pp:NaN649-649
Publication Date(Web):2014/10/27
DOI:10.1039/C4CY00871E
This review mainly summarizes our latest progress in the preparation of free-standing mesoporous metal catalysts and their applications in heterogeneous enantioselective hydrogenations. Owing to exclusion of the support effect, free-standing mesoporous metal could be a suitable experimental model for a mechanistic understanding, which would have significant benefits for the design of real catalysts with high performance. We start with a brief survey on the main synthetic approaches available for the preparation of free-standing mesoporous metal catalysts. Next, we select a few mesoporous metal catalysts to demonstrate their improved catalytic performance in the enantioselective hydrogenation of ketones or aromatic ketones. The factors influencing the activity and enantioselectivity, such as the modification conditions and confinement effect, are discussed. Finally, we introduce DFT calculations to gain insight into the molecular interaction involved in the adsorption process. We conclude the review with a personal perspective on the challenges and opportunities for the future development of efficient heterogeneous enantioselective metal catalysts.
Co-reporter:Yichen Hu, Bin Guo, Yingyi Fu, Yuanhang Ren, Gangfeng Tang, Xueying Chen, Bin Yue and Heyong He
Chemical Communications 2015 - vol. 51(Issue 75) pp:NaN14222-14222
Publication Date(Web):2015/08/10
DOI:10.1039/C5CC04548G
Sulfated titania solid superacids with dominant {001}, {001}/{101}, and {101} facets were prepared by the hydrothermal method and subsequent sulfation. Their facet-dependent acidic properties were investigated by the solid-state 31P NMR technique and Pechmann condensation of 5,7-dihydroxy-4-methyl coumarin.
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