- Exploiting Diffusion Barrier and Chemical Affinity of Metal-Organic Frameworks for Efficient Hydrogen Isotope Separation
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Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ～26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D2 through direct selective separation studies using 1:1 D2/H2 mixtures.
- Kim, Jin Yeong,Balderas-Xicohténcatl, Rafael,Zhang, Linda,Kang, Sung Gu,Hirscher, Michael,Oh, Hyunchul,Moon, Hoi Ri
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- Interfacially bonded CuCo2O4/TiO2 nanosheet heterostructures for boosting photocatalytic H2 production
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Constructing high-performance, economical and environmentally friendly photocatalysts remains a challenge for the efficient conversion of solar energy. In this work, CuCo2O4 nanoparticles modified on TiO2 nanosheets have b
- Xu, Chenhui,Jin, Chenyang,Chang, Wenxi,Hu, Xiaoyun,Deng, Hui,Liu, Enzhou,Fan, Jun
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- A water-based and high space-time yield synthetic route to MOF Ni2(dhtp) and its linker 2,5-dihydroxyterephthalic acid
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2,5-Dihydroxyterephthalic acid (H4dhtp) was synthesized on an 18 g scale by carboxylation of hydroquinone in molten potassium formate. The hydrated form of the Ni2(dhtp) MOF (also known as CPO-27-Ni and MOF-74(Ni)) was obtained in 92% yield by refluxing for 1 h a water suspension of the H4dhtp linker with an aqueous solution of nickel acetate. The ensuing characterization of the material (XRD, HRTEM, TGA, N2 adsorption at 77 K-SBET = 1233 m2 g-1) confirmed the formation of a metal-organic framework of at least equal quality to the ones obtained from the previously reported routes (CPO-27-Ni and MOF-74(Ni)), with a different morphology (namely, well-separated 1 ??m platelets for the herein reported water-based route). The temperature dependence of the magnetic susceptibility was measured and satisfactorily simulated assuming a Heisenberg (H = -2JΣSiSi+1) ferromagnetic intrachain interaction (J = +8.1 cm-1) and an antiferromagnetic interchain interaction (J′ = -1.15 cm-1). Overall, the reaction in water appears to follow easily distinguishable steps, the first being the deprotonation of H4dhtp by an acetate counterion, leading to a soluble nickel adduct of the linker, en route to the MOF self-assembly. This journal is
- Cadot, Stphane,Veyre, Laurent,Luneau, Dominique,Farrusseng, David,Alessandra Quadrelli, Elsje
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- Plasmonic Enhanced Reactive Oxygen Species Activation on Low-Work-Function Tungsten Nitride for Direct Near-Infrared Driven Photocatalysis
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Realizing near-infrared (NIR) driven photocatalytic reaction is one of the promising strategies to promote the solar energy utilization and photocatalytic efficiencies. However, effective reactive oxygen species (ROS) activation under NIR irradiation remains to be great challenge for nearly all previously reported photocatalysts. Herein, the cubic-phase tungsten nitride (WN) with strong plasmonic NIR absorption and low-work function (≈3.59?eV) is proved to be able to mediate direct ROS activation by both of experimental observation and theoretical simulation. The cubic WN nanocubes (NCs) are synthesized via the hydrothermal-ammonia nitridation process and its NIR-driven photocatalytic properties, including photocatalytic degradation, hydroxylation, and de-esterification, are reported for the first time in this work. The 3D finite element simulation results demonstrate the size dependent and wavelength tuned plasmonic NIR absorption of the WN NCs. The NIR-driven photocatalytic mechanism of WN NCs is proposed based on density functional theory (DFT) calculated electronic structure and facet dependent O2 (or H2O) molecular activation, radicals scavenging test, spin trapped electron paramagnetic resonance measurements, and ultraviolet photoelectronic spectrum (UPS). Overall, the results in this work pave a way for the application of low-work-function materials as highly reactive NIR photocatalyst.
- Huang, Weicheng,Gao, Yan,Wang, Jinxin,Ding, Pengcheng,Yan, Mei,Wu, Fengmin,Liu, Jian,Liu, Danqing,Guo, Chongshen,Yang, Bin,Cao, Wenwu
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- Coordinated Molecule-Modulated Magnetic Phase with Metamagnetism in Metal-Organic Frameworks
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Most well-known metal-organic frameworks (MOFs) possessing the magnetic Ni2O2(CO2)2 chains, called Ni-MOF-74, have been investigated with regard to magnetic properties at open-metal sites. We present the modulat
- Son, Kwanghyo,Kim, Jin Yeong,Schütz, Gisela,Kang, Sung Gu,Moon, Hoi Ri,Oh, Hyunchul
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- Method for preparing 2,5-dihydroxyl terephthalic acid (DHTA)
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The invention discloses a method for preparing 2,5-dihydroxyl terephthalic acid (DHTA). The invention relates to a method for preparing 2,5-dihydroxyl terephthalic acid (DHTA) by oxidizing dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate (DMSS). According to the method, hydrogen peroxide is adopted as an oxidizing agent, so that the oxide can be completely oxidized, the reactant conversion rate is high, the selectivity is relatively good, and the purity and yield of the target product are relatively high. In addition, hydrogen peroxide is converted into water after being oxidized, and byproducts formed by excessive oxidation do not exist in a reaction system. Therefore, the invention provides an economical and environment-friendly method for preparing 2,5-dihydroxyl terephthalic acid (DHTA), and the reaction is easy to control.
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Paragraph 0016; 0027-0028; 0029-0030; 0031-0032
(2021/04/10)
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- Metallic tungsten carbide nanoparticles as a near-infrared-driven photocatalyst
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Employing near infrared (NIR) light for photocatalytic reactions is preferable, considering effective solar utilization. Herein, the metalloid of tungsten carbide (WC) was used as an NIR-driven photocatalyst for the photodegradation of organic pollutants for the first time. The noble metal-like electronic properties of WC were proven via the analysis of its electronic occupied state using ultraviolet photoelectron spectroscopy and valence band XPS. In addition, both the experimental evidence and 3D finite element simulation revealed the NIR-responsive localized surface plasmon resonance (LSPR) behavior of the WC nanoparticles. Accordingly, the WC nanoparticles exhibited excellent UV-visible-NIR full-spectrum absorption, high NIR-triggered photocurrent response and resultant NIR-driven photocatalytic degradation performance. The NIR-mediated photocatalytic mechanism of WC was proposed based on a radical scavenging test, fluorescence observation of radical generation and spin-trapping electron paramagnetic resonance measurements. Hence, metallic WC with NIR absorption and photocatalytic activity may pave the way for the design of full-solar-spectrum-responsive photocatalysts.
- Huang, Weicheng,Meng, Hongxue,Gao, Yan,Wang, Jinxin,Yang, Chunyu,Liu, Danqing,Liu, Jian,Guo, Chongshen,Yang, Bin,Cao, Wenwu
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p. 18538 - 18546
(2019/08/12)
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- Discovery of novel 2,5-dihydroxyterephthalamide derivatives as multifunctional agents for the treatment of Alzheimer's disease
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A series of 2,5-dihydroxyterephthalamide derivatives were designed, synthesized and evaluated as multifunctional agents for the treatment of Alzheimer's disease. In vitro assays demonstrated that most of the derivatives exhibited good multifunctional activities. Among them, compound 9d showed the best inhibitory activity against both RatAChE and EeAChE (IC50 = 0.56 μM and 5.12 μM, respectively). Moreover, 9d exhibited excellent inhibitory effects on self-induced Aβ1–42 aggregation (IC50 = 3.05 μM) and Cu2+-induced Aβ1–42 aggregation (71.7% at 25.0 μM), and displayed significant disaggregation ability to self- and Cu2+-induced Aβ1–42 aggregation fibrils (75.2% and 77.2% at 25.0 μM, respectively). Furthermore, 9d also showed biometal chelating abilities, antioxidant activity, anti-neuroinflammatory activities and appropriate BBB permeability. These multifunctional properties highlight 9d as promising candidate for further studies directed to the development of novel drugs against AD.
- Song, Qing,Li, Yan,Cao, Zhongcheng,Liu, Hongyan,Tian, Chaoquan,Yang, Ziyi,Qiang, Xiaoming,Tan, Zhenghuai,Deng, Yong
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p. 6115 - 6127
(2018/11/23)
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- TD-DFT Investigation of 2,5-Bis(2-benzothiazolyl)hydroquinone and 2,5-Bis(benzo[d]thiazol-2-yl)-4-methoxyphenol
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Density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations of two excited state intramolecular proton transfer (ESIPT) molecules [2,5-bis(2-benzothiazolyl)hydroquinone and 2,5-bis(benzo[d]thiazol-2-yl)-4-methoxyphenol] were performed to study their structural and photo-physical behavior upon excitation. The most stable structure was established by optimizing all possible rotamers. The vertical excitation and emission wavelengths obtained by using TD-DFT show very good correlation with the experimental values. A correlation has been established based on the absorption values to determine the contribution of stable rotamers.
- Jadhav, Manoj M.,Alswaidan, Ibrahim A.,Rhyman, Lydia,Ramasami, Ponnadurai,Sekar, Nagaiyan
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p. 1005 - 1023
(2017/05/29)
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- Unfolding ESIPT in Bis-2,5-(2-benzoxazolyl) Hydroquinone and 2,5-Bis(benzo[d]oxazol-2-yl)-4-methoxyphenol: a Comprehensive Computational Approach
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The photo-physical behaviour of bis-2,5-(2-benzoxazolyl) hydroquinone and 2,5-bis (benzo[d]oxazol-2-yl)-4-methoxyphenol was studied using the Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT). All the possible rotamers were optimized to obtain global minimum optimized structure. The theoretical absorption and emission values of rotamers estimated by using TD-DFT [TD-B3LYP/6–31G(d)] are in good agreement with experimental absorption and emission wavelengths. Based on the absorption values, the contribution of respective rotamer is determined theoretically.
- Jadhav, Manoj M.,Rhyman, Lydia,Ramasami, Ponnadurai,Sekar, Nagaiyan
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p. 1295 - 1307
(2016/07/30)
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- Mn2(2,5-disulfhydrylbenzene-1,4-dicarboxylate): A microporous metal-organic framework with infinite (-Mn-S-)∞ chains and high intrinsic charge mobility
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The reaction of MnCl2 with 2,5-disulfhydrylbenzene-1,4- dicarboxylic acid (H4DSBDC), in which the phenol groups in 2,5-dihydroxybenzene-1,4-dicarboxylic acid (H4DOBDC) have been replaced by thiophenol units, led to the isolation of Mn2(DSBDC), a thiolated analogue of the M2(DOBDC) series of metal-organic frameworks (MOFs). The sulfur atoms participate in infinite one-dimensional Mn-S chains, and Mn2(DSBDC) shows a high surface area and high charge mobility similar to that found in some of the most common organic semiconductors. The synthetic approach to Mn2(DSBDC) and its excellent electronic properties provide a blueprint for a potentially rich area of exploration in microporous conductive MOFs with low-dimensional charge transport pathways.
- Sun, Lei,Miyakai, Tomoyo,Seki, Shu,Dinca, Mircea
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supporting information
p. 8185 - 8188
(2013/07/05)
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- PROCESS FOR PREPARING 2,5-DIHYDROXYTEREPHTHALIC ACID
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The present invention provides a process for preparing 2,5-dihydroxyterephthalic acid which comprises reacting a dialkali metal salt of hydroquinone with carbon dioxide in a reaction medium in the presence of a potassium salt represented by formula (I): [in-line-formulae]CnH2n+1COOK??(I)[/in-line-formulae] wherein n is an integer of 1-17. According to the process for preparing 2,5-dihydroxyterephthalic acid of the present invention, 2,5-dihydroxyterephthalic acid can be produced both safely and at a low cost under industrially advantageous conditions. Further, the process according to the present invention causes less damage to reaction equipment and the like.
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Page/Page column 3
(2012/12/14)
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- Functionalization in flexible porous solids: Effects on the pore opening and the host-guest interactions
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The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and 57Fe Moessbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)2) exhibits a nitrogen accessible porosity (SBET ≈ 100 m2 g-1). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.
- Devic, Thomas,Horcajada, Patricia,Serre, Christian,Salles, Fabrice,Maurin, Guillaume,Moulin, Beatrice,Heurtaux, Daniela,Clet, Guillaume,Vimont, Alexandre,Greneche, Jean-Marc,Le Ouay, Benjamin,Moreau, Florian,Magnier, Emmanuel,Filinchuk, Yaroslav,Marrot, Jerome,Lavalley, Jean-Claude,Daturi, Marco,Ferey, Gerard
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supporting information; experimental part
p. 1127 - 1136
(2010/04/01)
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- Process for the synthesis of hydroxy aromatic acids
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Hydroxy aromatic acids are produced in high yields and high purity (>95%) from halogenated aromatic acids in a reaction mixture containing a copper source and a ligand that coordinates to copper.
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Page/Page column 10-11
(2008/06/13)
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- Process for the synthesis of hydroxy aromatic acids
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Hydroxy aromatic acids are produced in high yields and high purity (>95%) from halogenated aromatic acids in a reaction mixture containing a copper source and a ligand that coordinates to copper.
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Page/Page column 22-23
(2008/06/13)
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- Process for the synthesis of 2,5-dihydroxyterephthalic acid
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2,5-dihydroxyterephthalic acid is produced in high yields and high purity from 2,5-dihaloterephthalic acid by contact with a copper source and a ligand that coordinates to copper under basic conditions.
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Page/Page column 19
(2008/06/13)
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- Process for the synthesis of 2,5-dihydroxyterephthalic acid
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2,5-dihydroxyterephthalic acid is produced in high yields and high purity from 2,5-dihaloterephthalic acid by contact with a copper source and a ligand that coordinates to copper under basic conditions.
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Page/Page column 8-9
(2008/06/13)
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- Process for the synthesis of 2,5-dihydroxyterephthalic acid
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2,5-dihydroxyterephthalic acid is produced in high yields and high purity from 2,5-dihaloterephthalic acid by contact with a copper source and a ligand that coordinates to copper under basic conditions.
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Page/Page column 9-10
(2008/06/13)
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- Process for the synthesis of 2,5-dihydroxyterephthalic acid
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2,5-dihydroxyterephthalic acid is produced in high yields and high purity from 2,5-dihaloterephthalic acid by contact with a copper source and a ligand that coordinates to copper under basic conditions.
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Page/Page column 9
(2008/06/13)
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- Process for the synthesis of hydroxy aromatic acids
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Hydroxy aromatic acids are produced in high yields and high purity (>95%) from halogenated aromatic acids in a reaction mixture containing a copper source and a ligand that coordinates to copper.
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Page/Page column 12
(2008/12/05)
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- Process for dicarboxylating dihydric phenols
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A process is disclosed for dicarboxylating dihydric phenols, notably those where the hydroxyl groups are in the para or the ortho position vis-+E,gra a+EE -vis one another. More particularly, the invention pertains to a process for preparing 2,5-dihydroxy
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