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1.
ACS Appl Mater Interfaces ; 16(5): 6367-6381, 2024 Feb 07.
Article in English | MEDLINE | ID: mdl-38270091

ABSTRACT

Herein, we present a distinct methodology for the in situ electrostatic assembly method for synthesizing a conjugated (IDT-COOH)/oxygen-doped g-C3N4 (O-CN) S-scheme heterojunction. The electron delocalization effect due to π-π interactions between O-CN and self-assembled IDT-COOH favors interfacial charge separation. The self-assembled IDT-COOH/O-CN exhibits a broadened visible absorption to generate more charge carriers. The internal electric field between the IDT-COOH and the O-CN interface provides a directional charge-transfer channel to increase the utilization of photoinduced charge carriers. Moreover, the active species (•O2-, h+, and 1O2) produced by IDT-COOH/O-CN under visible light play important roles in photocatalytic disinfection. The optimum 40% IDT-COOH/O-CN can kill 7-log of methicillin-resistant Staphylococcus aureus (MRSA) cells in 2 h and remove 88% tetracycline (TC) in 5 h, while O-CN only inactivates 1-log of MRSA cells and degrades 40% TC. This work contributes to a promising method to fabricate all-organic g-C3N4-based S-scheme heterojunction photocatalysts with a wide range of optical responses and enhanced exciton dissociation.

2.
Dalton Trans ; 52(43): 15767-15774, 2023 Nov 07.
Article in English | MEDLINE | ID: mdl-37847404

ABSTRACT

Hydrogen economy has emerged as a promising alternative to the current hydrocarbon economy. It involves harvesting renewable energy to split water into hydrogen and oxygen and then further utilising clean hydrogen fuel for various applications. The rational exploration of advanced non-precious metal bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is critical for efficient water splitting. Herein, an ultralow Ru-modified cobalt metal-organic framework (CoRu0.06-MOF/NF) two-dimensional nanosheet array bifunctional catalyst was fabricated through a strategy under mild experimental conditions. The obtained CoRu0.06-MOF/NF exhibited excellent bifunctional electrocatalytic activity and stability in alkaline media, with low overpotentials of 37 and 181 mV and significant durability for more than 95 and 110 h toward the HER and OER at 10 mA cm-2, respectively. The experimental results showed that the two-dimensional nanoarray structure had a large specific surface area and abundant exposed active sites. Additionally, ultralow Ru modification optimized the electronic structure and improved the conductivity of the cobalt metal-organic frameworks, thereby reducing the energy barrier of the rate-limiting step and accelerating the water splitting reaction.

3.
Molecules ; 28(11)2023 May 25.
Article in English | MEDLINE | ID: mdl-37298822

ABSTRACT

Regio- and stereoselective switchable synthesis of (E)- and (Z)-N-carbonylvinylated pyrazoles is first developed by using the Michael addition reaction of pyrazoles and conjugated carbonyl alkynes. Ag2CO3 plays a key role in the switchable synthesis of (E)- and (Z)-N-carbonylvinylated pyrazoles. Ag2CO3-free reactions lead to thermodynamically stable (E)-N-carbonylvinylated pyrazoles in excellent yields whereas reactions with Ag2CO3 give (Z)-N-carbonylvinylated pyrazoles in good yields. It is noteworthy that (E)- or (Z)-N1-carbonylvinylated pyrazoles are obtained with high regioselectivity when asymmetrically substituted pyrazoles react with conjugated carbonyl alkynes. The method can also extend to the gram scale. A plausible mechanism is proposed on the basis of the detailed studies, wherein Ag+ acts as coordination guidance.


Subject(s)
Alkynes , Pyrazoles , Stereoisomerism , Catalysis
4.
Sci Rep ; 13(1): 237, 2023 01 05.
Article in English | MEDLINE | ID: mdl-36604577

ABSTRACT

A 1:10 scale model tunnel with a length, height and width of 9 m, 0.6 m and 0.8 m, respectively, was set up in this paper. A water curtain system was installed in the model to investigate the effect of water curtain systems on smoke flow and heat propagation. A reduced-scale experimental and theoretical study was carried out by varying the heat release rate of the fire source, the water curtain pressure, and the number of water curtain rows. A series of tests were carried out for various setups to quantify each mechanism of interaction between the water mist and hot smoke, to propose a method for qualitatively analysing water curtain systems blocking the propagation of heat radiation and the flow of smoke from combustion, and to propose a method for predicting heat fluxes. The study found that the pressure of the water curtain, the number of rows, and the heat release rate of the fire source all had an effect on the smoke blocking effect of the water curtain system. This effect decreased as the heat release rate of the fire source increased and increased significantly with the pressure of the water curtain and the number of rows. The smoke blocking effect was quantified using conservation of momentum by establishing a dimensionless parameter R to represent the ratio of water curtain momentum to smoke momentum, as well as the ratio of heat flux before and after the water curtain to represent the smoke blocking capacity [Formula: see text] of the water curtain. The smoke blockage rate [Formula: see text] ranges between 40 and 75%, and the smoke blockage rate increases as the momentum R increases. Finally, in tunnel fires, a predictive model for the attenuation of heat radiation by water curtains has been developed, providing theoretical support for the quantitative study of the smoke and thermal blockage effects of water curtains, which is beneficial to the protection of human life in confined spaces.


Subject(s)
Fires , Water , Humans , Hot Temperature , Models, Theoretical
5.
Dalton Trans ; 52(3): 754-762, 2023 Jan 17.
Article in English | MEDLINE | ID: mdl-36562484

ABSTRACT

In this work, a novel anionic Cd-MOF ([(CH3)2NH2]n[Cd(HL)DMF]n·2nH2O·nDMF, H4L = 1,2,4,5-tetrakis[(4-carboxy)phenoxymethyl]benzene) was synthesized for the first time. As a precursor, it was utilized to obtain Fe@Cd-MOF crystals via the substitution of Fe3+ ions due to a negatively charged framework and free-coordinated carboxyl group. Fe3O4/Fe-embedded carbon-based materials (Fe@Cd-MOFD) were further constructed by deriving Fe@Cd-MOF at high temperatures. The derived Fe@Cd-MOFD showed a structure resembling a central city with metal redox centers embedded into a carbon matrix. The introduced Fe3+ ions formed a local nano-sized metal oxide upon annealing, and these derived carbon materials offered high electronic conductivity. These pushed Fe@Cd-MOFD to remarkable electrochemical performance with an initial discharge capacity of 1703.8 mA h g-1. This work offers new insights into the fabrication of novel MOF-derived iron oxide hybrids for lithium storage.

6.
J Colloid Interface Sci ; 632(Pt B): 285-298, 2023 Feb 15.
Article in English | MEDLINE | ID: mdl-36427423

ABSTRACT

To adequately utilize solar energy for water pollution remediation, tailoring graphite carbon nitride (CN) with sufficient active sites exposure, visible-light harvest and eminent charge separation/migration/recombination efficiency, has long been pursuing. Herein, a pyrazine doped distorted architecture CN with advancing n-π* electron transition was tailored via one-pot thermal-melting assemble following thermal-induce copolymerization of pyrazine-2,3-dicarboxylic acid and urea. Various characterizations verify the successful construction of distorted porous thin wall CN. The nitrogen adsorption-desorption, photoelectric and band structure analysis manifest that the optimized 20-PACN sample possesses propelled visible-light capture ability with wavelength above 500 nm, more active sites exposure with high specific surface area and hybrid electron structure with distinctly improved charge separation/migration/recombination efficiency. More importantly, 10 mg of 20-PACN can photodegradation 97 % of tetracycline (91 % of rhodamine B or 91 % of methylene blue) within 100 min, which is 7.1 times of bulk counterparts. ESR and quenching tests confirm that apart from h+, ⋅O2- and 1O2 significantly assist to the photodegradation reaction, which profit from upshifted CB and the appearance of intermediate state. The mass spectrum, toxicity prediction and on-line infrared spectroscopy explicated intermediates, routes and toxicity, as well as real-time monitor the variation of functional groups during photodegradation reaction. At last, combined the above test characterization and density functional theory analysis, a potential propelled mechanism of photodegradation was proposed.


Subject(s)
Electrons , Nitrogen , Photolysis , Pyrazines
7.
ACS Omega ; 7(44): 40419-40431, 2022 Nov 08.
Article in English | MEDLINE | ID: mdl-36385859

ABSTRACT

Transport belt fires pose a serious threat to the lives of miners. The smoke spread characteristics of transport belt fires are important for the effective construction of underground safety works. In this paper, a water curtain system is added to ventilation to investigate the effectiveness of water spray in blocking fire-induced smoke and heat. Using computational fluid dynamics (CFD) simulations obtained with FDS 6.0.1, full-scale underground belt transport tunnel fire tests are conducted with mechanical ventilation and a water curtain system to obtain smoke spread characteristics, temperature distribution, visibility profiles, and CO distribution. The results show that the addition of a water curtain system can effectively limit temperature and smoke, but high mechanical ventilation velocities are not conducive to the water curtain system, limiting underground tunnel fires. This study found that the mechanical ventilation velocity should be controlled at approximately 0.8 m/s when the water curtain system is on a 100 m beltway. Smoke across the water curtain system area, smoke stratification in the lower layer of the water curtain area is lost, the water curtain system in the lower layer of the tunnel will affect the flow field and temperature field flowing to the fire source, and the blockage effect is the most obvious in the upper layer of the tunnel. The water curtain system reduces the distribution of temperature and CO concentration in the tunnel and rapidly restores visibility. With the addition of the water curtain system, the environment in the restricted area is suitable for occupant evacuation and firefighting, and the system can be considered a viable strategy for tunnel smoke control.

8.
Inorg Chem ; 61(34): 13453-13461, 2022 Aug 29.
Article in English | MEDLINE | ID: mdl-35969492

ABSTRACT

It is a challenge to fabricate atomically dispersed metal clusters in polymeric carbon nitride (PCN) for durable photocatalytic reactions owing to the thermodynamic stability limitation. Herein, atomically dispersed Ru clusters are implanted into the PCN skeleton matrix based on an ionic diffusion and coordination (IDC) strategy, the stability of which is improved owing to the robust Ru-N bonds in the formed RuN4 and RuN3 configurations. Additionally, RuN4 and RuN3 as charge transport bridges between two adjacent melon strands efficaciously conquer hydrogen bond restriction in the skeleton to facilitate the in-plane mobility and separation of charge carriers. Moreover, the synergistic effect of adjacent Ru atoms is triggered on the assembled RuN3-RuN4 and RuN3-RuN3 in the atomically dispersed Ru clusters to significantly decrease hydrogen adsorption energy. As a result, the optimal PCN-Ru photocatalyst achieves nearly 6 times higher than the photocatalytic hydrogen evolution (PHE) rate of the Pt/PCN benchmark and maintains the long-term stable running for 104 h of 26 cycles; its overall PHE performance is far superior to the most of single atoms supported on g-C3N4 photocatalysts reported. The findings here gain new insight into the preparation strategy, structure configuration, and reaction mechanism for atomically dispersed metal clusters supported on PCN, which further stimulates the intensive investigations toward developing more efficient and stable PCN-like photocatalytic materials.

9.
Spectrochim Acta A Mol Biomol Spectrosc ; 281: 121587, 2022 Nov 15.
Article in English | MEDLINE | ID: mdl-35797948

ABSTRACT

In this test, the eggshell membrane (ESM) is selected as the support membrane for the biocompatibility and anchors CNTs on the surface to increase the mechanical properties. Then Ag NPs are decorated on CNTs-ESM substrate as SERS substrate by twice in-situ reduction. Finally, a layer of imprinted polymers is coated on the surface of the substrate to synthesize the imprinted membrane for selective detection of spiramycin. It is exhibited from the characteristic results that the CNTs significantly increase the mechanical properties and the detection sensitivity, simultaneously. When the concentration of SP changes between 10-6 âˆ¼ 10-11 M, there is a linear relationship between SERS intensity and SP concentration. The detection limit is 10-11 M, and the correlation coefficient R2 is 0.9864. The SERS imprinted membrane can be applied into the detection of antibiotics in practical sample, which broadens the research field of antibiotics detection.


Subject(s)
Molecular Imprinting , Spiramycin , Anti-Bacterial Agents , Molecular Imprinting/methods , Polymers/chemistry , Spectrum Analysis, Raman/methods
10.
Dalton Trans ; 51(24): 9486-9494, 2022 Jun 21.
Article in English | MEDLINE | ID: mdl-35678597

ABSTRACT

The advancement of a bifunctional electrocatalyst consisting of Earth's rich elements and exhibiting high efficiency is the key to obtain hydrogen fuel by overall water splitting (OWS). Here, a facile and extensible hydrothermal synthesis of an electrocatalyst on iron foam (MoOx/Fe1-xS/IF) as a robust bifunctional catalyst with excellent catalytic activity is designed for the hydrogen evolution reaction (HER) with an overpotential of 142 mV at 100 mA cm-2, and for the OER with lower overpotentials of 300 and 500 mV at 100 and 1000 mA cm-2. The good activity is ascribed to the controllable morphology, stronger bonding of the catalyst to a substrate and optimized electronic configuration. When used as bifunctional electrocatalysts toward alkaline overall water splitting, MoOx/Fe1-xS/IF delivers a current density of 10 mA cm-2 at a low cell voltage of 1.56 V for 110 h. Such high performance coupled with low-cost iron-based materials suggests that the present strategy may open new avenues for the rational design of electrocatalysts and for use in practical water splitting.

11.
J Colloid Interface Sci ; 614: 532-537, 2022 May 15.
Article in English | MEDLINE | ID: mdl-35121511

ABSTRACT

Evidence shows that self-supported electrocatalysts are crucial role to solving environmental and energy issues. In this study, self-supported 2D metal-organic framework (MOF) nanosheets grown in situ on nickel-iron foam (NFF) were prepared by a one-step solvothermal process. The hierarchical nanostructure possesses a high specific surface area and abundant metal sites, which are beneficial for electrocatalytic reactions. In the electrocatalytic oxygen evolution reaction (OER), the optimal NiFe(20Ni)-MOF/NFF can drive current densities of 10, 50 and 100 mA cm-2 at small overpotentials of 226, 277 and 294 mV, respectively. According to the characterization results, the OER performance is improved by the synergistic action of bimetals and the generation of hydroxides/oxyhydroxides. This work provides new insights into fabricating self-supported MOF-based electrodes for water splitting that are simple and highly efficient.

12.
J Mater Chem B ; 10(5): 737-747, 2022 02 02.
Article in English | MEDLINE | ID: mdl-35022631

ABSTRACT

The low utilization of visible light and the fast recombination of photogenerated electron-hole pairs are the two intrinsic defects that have hindered the antibacterial applications of TiO2. The addition of organic photocatalytic agents to form heterojunctions with TiO2 powder can effectively address these problems. A novel linear conjugated polymer poly[(thiophene-ethylene-thiophene)-thiophene-3-carboxylic acid decyl ester] (PTCD) was successfully synthesized via Stille coupling polymerization. PTCD and TiO2 can form a heterojunction photocatalyst (PTCD/TiO2), and this product was characterized using NMR and XRD. The UV-vis spectra showed that the absorption edge of the PTCD/TiO2 heterojunction extends to approximately 700 nm, which indicates that the visible-light utilization is greatly improved. Staphylococcus aureus (S. aureus) was selected as the target organism to test the photocatalytic antimicrobial activity of the material. Photogenerated electrons can undergo directional transmission of the PTCD polymer to TiO2 on the PTCD/TiO2 heterojunction to realize excellent antibacterial properties. With an optimized PTCD loading ratio of 30%, PTCD/TiO2 showed an antibacterial rate that was 14.5 times greater than that of pure TiO2 in 4 h under visible-light irradiation.


Subject(s)
Polymers , Staphylococcus aureus , Anti-Bacterial Agents/pharmacology , Catalysis , Light , Polymers/pharmacology , Thiophenes/pharmacology , Titanium
13.
ACS Appl Mater Interfaces ; 14(5): 7082-7092, 2022 Feb 09.
Article in English | MEDLINE | ID: mdl-35076207

ABSTRACT

Selenium-heterocyclic and side-chain strategies for developing near-infrared (NIR) small fused-ring acceptors (FRAs) to further obtain short-circuit current density (Jsc) have proven advantageous in the top-performing polymer solar cells (PSCs). Herein, a new electron-rich central selenium-containing heterocycle core (BTSe) attaching alkyl side chains with a terminal phenyl group was coupled with a difluorinated and dichlorinated electron-accepting terminal 1,1-dicyanomethylene-3-indanone (IC) to afford two types of new FRAs, BTSe-IC2F and BTSe-IC2Cl. Interestingly, in spite of the weaker intramolecular charge transfer, BTSe-IC2F shows a stronger NIR response because of the smaller bandgap (Egopt) up to 1.26 eV, benefiting from the stronger ordered molecular packing in comparison to BTSe-IC2Cl with an Egopt of 1.30 eV. Additionally, thermal annealing induced an evident red shift by ∼50 nm in the absorption of D18:BTSe-IC2F blend films. Such a phenomenon may be attributed to the synergistic impact of the formation of inward constriction toward the molecular backbone because of the combination of bulky side chains and fluorinated IC as well as the reduced aromaticity of the selenium heterocycle. Consequently, the thermally annealed device based on BTSe-IC2F/D18 achieves a champion power conversion efficiency (PCE) of 17.3% with a high fill factor (FF) of 77.22%, which is among the highest reported PCE values for selenium-heterocyclic FRAs in binary PSCs. The improved Jsc and FF values of the D18:BTSe-IC2F film are simultaneously achieved mainly because of the preferred face-on orientations, the well-balanced electron/hole mobility, and the favorable blend morphology compared to D18:BTSe-IC2Cl. This work suggests that the selenium-heterocyclic fused-ring core (with proper side chains) combined with fluorinated terminal groups is an effective strategy for obtaining highly efficient NIR-responsive FRAs.

14.
J Environ Manage ; 304: 114260, 2022 Feb 15.
Article in English | MEDLINE | ID: mdl-34915386

ABSTRACT

The polyvinylidene difluoride (PVDF) membrane has received considerable attention as a flexible surface enhanced Raman scattering (SERS) substrate due to its excellent mechanical and physicochemical properties. However, the poor fouling resistance of PVDF membrane due to its intrinsic hydrophobic property limits its practical application. To address this, in this investigation, a SERS imprinted membrane is synthesized based on W18O49/Ag composites. Firstly, to promote hydrophilicity, N-vinyl-2-pyrrolidone (NVP) and triethoxyvinylsilane (VTES) are copolymerized by hydrolysis condensation and linked with engineered polyvinypyrrolidone (PVP) chains exposed on the surface of membrane. Furthermore, W18O49/Ag composites are dispersed on the membrane under the assistance of polydopamine (pDA) to promote the pollution resistance. Subsequently, in order to demonstrate the practical detection property, W18O49/Ag/PVDF membrane is selected as the SERS substrate to synthesize SERS imprinted membrane by precipitation polymerization for the selective detection of L-tyrosine. The characteristic results reveal that the SERS-imprinted membrane exhibits satisfactory hydrophilicity, and it can effectively degrade the pollutant molecules absorbed on its surface under ultraviolet light illumination. It is proved from the detection results that the LOD of WADP-MIMs for L-tyrosine reached 10-9 mol L-1 when the concentration of L-tyrosine changed between 10-3-10-9 mol L-1. The correlation coefficient (R2) is 0.994 and the limit of detection is 10-9 mol L-1. Meanwhile, it can be applied for the selective detection of L-tyrosine in mixture samples. Overall, this study presents a novel approach for the hydrophilic modification and pollution resistance enhancement of PVDF-based SERS imprinted membrane, which can be effectively utilized for the selective detection of practical samples.


Subject(s)
Polyvinyls , Tyrosine , Fluorocarbon Polymers , Hydrophobic and Hydrophilic Interactions , Spectrum Analysis, Raman
15.
ACS Appl Mater Interfaces ; 13(43): 51447-51458, 2021 Nov 03.
Article in English | MEDLINE | ID: mdl-34676747

ABSTRACT

Herein, a novel donor-acceptor (D-A) conjugated linear polymeric system, poly[(2,6-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-2,5-(3-carboxyl)-thiophene] (PBDT-F-COOH), with outstanding processing ability and its all-organic PBDT-F-COOH coating featuring chemical bonding for combination with polyurethane were prepared. Wide visible spectrum-driven PBDT-F-COOH and PBDT-F-COOH-PU showed dual efficient photocatalytic activities toward degradation and disinfection, mainly attributing to efficient dissociation of excitons and transfer of charge carriers, resulting from the large dipole moment of D-A PBDT-F-COOH. PBDT-F-COOH demonstrated >99.2% inactivation of Staphylococcus aureus (S. aureus) within 1 h and a 7-log decrease in 4 h under visible light irradiation. Additionally, the coating showed the 7-log inactivation of S. aureus in 7 h. These inactivation efficiency results are among those of the best reported D-A conjugated linear polymers. Importantly, PBDT-F-COOH and the PBDT-F-COOH-PU coating both presented satisfactory stability with high photocatalytic activity after recycling runs. This work provides a feasible approach for fabricating nontoxic and highly active organic photocatalysts with wide visible spectra and a large dipole moment via a D-A linear structure design protocol.

16.
Sci Rep ; 11(1): 21204, 2021 Oct 27.
Article in English | MEDLINE | ID: mdl-34707179

ABSTRACT

To explore the overpressure evolution laws and flame propagation characteristics in complex pipe networks after the addition of hydrogen to methane, we experimentally studied the explosive pressure wave and flame wave propagation laws for three different premixed gas mixtures with hydrogen-methane concentrations of 0, 10% and 20% when the equivalence ratio was 1. Experimental results indicate that the maximum explosion overpressure of the premixed gas increases with increasing distance from the explosion source, and it shows a gradually decreasing trend. In the complex pipe network, an overpressure zone is formed in the B-E-H and D-E sections of the network. The flame temperature is superimposed with the superimposition of the pressure, showing a trend of first increasing, then decreasing, then increasing, and finally decreasing in the complex pipe network. The flame arrival time increases with increasing distance, and the maximum flame speed shows a decreasing trend. The peak overpressure and maximum flame velocity of the premixed gas under a hydrogen volume fraction of 20% are 1.266 MPa and 168 m/s. The experimental research results could provide important theoretical guidelines for the prevention and control of fuel gas explosions in urban pipe networks.

17.
Nanoscale ; 13(42): 17953-17960, 2021 Nov 04.
Article in English | MEDLINE | ID: mdl-34698752

ABSTRACT

Developing efficient and promising non-noble catalysts that can promote both the HER and OER in the same electrolyte is vital. Currently, these reported bifunctional catalysts show only moderate electrocatalytic water-splitting performance, which is much lower than expected. In addition, most of these promising nonprecious electrocatalysts work well only at small current densities (e.g. 10 mA cm-1), but at large current densities their stability and activity are far from satisfactory for practical applications. Herein, we have successfully constructed an urchin-like Ni3S2@Ni3B heterostructure electrocatalyst on Ni plates. The resulting material exhibits great catalytic activities for both the HER and OER, even at large current densities, reaching a current density of 1000 mA cm-l at relatively low applied overpotentials of 517 and 632 mV, respectively. The excellent catalytic performance of Ni3S2@Ni3B/NP is found to benefit from the effective integration of the unique surface structure and the interface electronic structure.

18.
Soft Matter ; 17(30): 7227-7235, 2021 Aug 05.
Article in English | MEDLINE | ID: mdl-34286804

ABSTRACT

A C3-symmetric acylhydrazone-based low molecular weight gelator (BHTP) bearing three pyridine units was synthesized and it was found to form a stable supramolecular gel in the mixture solvent of DMSO-H2O. The morphology of the gel as observed by FE-SEM showed a dense sheet structure. Hydrogen bonding and π-π stacking between the gelators were determined as the non-covalent interactions for the gelation, which were investigated thoroughly using XRD, UV-Vis, 1H NMR and FT-IR instruments. BHTP could form pH tolerant supramolecular gels in the widest range of pH values from 1 to 11. The DMSO-H2O (v : v = 1 : 1) gel exhibited selective response to OH- over a series of other anions through the color change from a white gel to a yellow solution, and the OH- response mechanism was proved by 1H NMR experiments. In solution, the lowest detection limit of BHTP for OH- was calculated to be as low as 1.62 × 10-7 M via UV-Vis titration experiments. Finally, encapsulation and controlled release of small molecules such as rhodamine B, crystal violet and methyl orange have been successfully carried out, demonstrating the potential for drug delivery application of this C3-symmetric supramolecular gel. This work opens a novel avenue for the preparation of supramolecular gel-based multiple functional smart materials.

19.
Dalton Trans ; 50(26): 9076-9087, 2021 Jul 06.
Article in English | MEDLINE | ID: mdl-34124728

ABSTRACT

Metastable Cu2O is an attractive material for the architectural design of integrated nanomaterials. In this context, Cu2O was used as the sacrificial agent to form the core-shell structure of Cu2O@HKUST-1 by in situ growth technology. The MOFs with BOPs adsorption property were gathered together by a Cu2O etching method, and the hollow structure of the HKUST-1 shell material with fast BOP adsorption was successfully constructed. The adsorption experiments showed that the HKUST-1 shell has a good adsorption effect on nitrobenzene pollutants in wastewater. The investigation of various factors affecting the adsorption, thermodynamic and kinetic equations was carried out. The adsorption equilibrium was reached within 30 min, and the maximum adsorption capacity was 94.67 mg g-1 at 298 K. The adsorption capacity of nitrobenzene by the HKUST-1 shell is in good agreement with the Freundlich model and the second-order kinetic model. The possible mechanism of adsorption of nitrobenzene by the HKUST-1 shell was discussed. The experimental results suggested that Cu-BTC materials have potential applications for wastewater treatment involving benzene pollutants.

20.
ACS Appl Mater Interfaces ; 13(11): 13254-13263, 2021 Mar 24.
Article in English | MEDLINE | ID: mdl-33689285

ABSTRACT

Inspired by the structural advantages of spiro-OMeTAD, which is the most commonly used hole-transporting material (HTM), two rationally designed HTMs with butterfly-shaped triarylamine groups based on dibenzofulvene-bridged indacenodithiophene (IDT) core (attaching hexyl and octyl chains) have been synthesized, namely, IT-C6 and IT-C8, respectively. Shorter alkyl-chain-based IT-C6 exhibits a marked increase in glass-transition temperature (Tg) of 105 °C, whereas IT-C8 shows a Tg of 95 °C. Moreover, it is demonstrated that IT-C6 exhibits a higher hole-transporting mobility, more suitable band energy alignment, better interfacial contact, and passivation effect. The inverted devices of employed HTM based on IT-C6 obtained a champion PCE of 18.34% with a remarkable fill factor (FF) of 82.32%, whereas the IT-C8-based device delivered an inferior PCE of 16.94% with an FF up to 81.20%. Both HTMs embodied inverted devices present high FF values greater than 81%, which are among the highest reported values of small molecular HTM-based PSCs. This work reveals that cutting off the symmetrical spiro-core and subsequently combining IDT (attaching tailored alkyl chains) with the spiro-linkage fluorine to construct the orthogonal molecular conformation is a significant principle for the design of promising dopant-free HTMs.

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