NiFe LDHs/MXene composites are preliminarily prepared by the hydrothermal method. Then, Ni nanoparticles/ LDHs/MXene ternary composites are formed by in-situ reduction by NaBH4 in liquid phase. Interfacial morphology and structure of Ni/LDHs/MXene composites are investigated by SEM, XRD, and XPS. For catalytic hydrogenation of p-nitrophenol (4-NP), the catalytic apparent rate (Kapp) of Ni/LDHs/MXene-4 sample can reach to 175.5 s-1 center dot g-1 and the actual conversion rate is close to 100% after 9 min. As a recyclable catalyst, the stability of catalytic hydrogenation can remain about 94.1 % after 7 cycles. These ternary composites may be potentially applied in the pharmaceutical intermediates and catalytic conversion.
The strength and micro-distance of acidic and basic sites on acid-base pair catalysts (ABPC) are crucial in determining their synergistic effect and catalytic capacity, yet challenging in the synthesis of effective ABPC due to the tunable difficulties. Here, a Co-ZnO ABPC, containing adjacent Co single atoms-ZnO nanocluster acid-base pairs, was prepared by pyrolyzing ZnCo ZIF-precursor under vacuum. Benefiting from the unique acid-base pair features, Co-ZnO ABPC exhibited outstanding performance for the catalytic hydrogen transfer (CHT) cascade reaction, achieving high nitrobenzene conversion (95 %) and imine selectivity (98 %) at 160 celcius for 3 h, exceeded almost all the documented catalysts. Both the experimental and calculation results verified the stronger acidity of Co SAs and the synergistic effect of acid-base sites lowered the free energy barrier. This work provides not only prospective insight into the effect of acid-base sites on the catalytic capacity but also a guide for the rational design of efficient ABPC.
Platinum-based anticancer drugs play a crucial role in the clinical treatment of various cancers. However, the application of platinum-based drugs is heavily restricted by their severe toxicity and drug resistance/cross resistance. Various drug delivery systems have been developed to overcome these limitations of platinum-based chemotherapy. Stimuli-responsive nanocarrier drug delivery systems as one of the most promising strategies attract more attention. And huge progress in stimuli-responsive nanocarrier delivery systems of platinum-based drugs has been made. In these systems, a variety of triggers including endogenous and extracorporeal stimuli have been employed. Endogenous stimuli mainly include pH-, thermo-, enzyme- and redox-responsive nanocarriers. Extracorporeal stimuli include light-, magnetic field- and ultrasound responsive nanocarriers. In this review, we present the recent advances in stimuli-responsive drug delivery systems with different nanocarriers for improving the efficacy and reducing the side effects of platinum-based anticancer drugs.
Photothermal catalysis has attracted great attention owing to high solar energy utilization efficiency, and great progress has been achieved in gas-phase catalysis. However, photothermal catalysis in liquid-phase shows a limited performance, due to high specific heat capacity of liquid. Herein, an interfacial photothermal catalytic (IPC) strategy applying an IPC leaf was designed for liquid-phase catalysis using benzyl alcohol oxidation as the model reaction. On even ground, the benzaldehyde generation rate (8.7 mmol g(cat)(-1) h(-1)) of the IPC system with Ce-doped MnO2 as photothermal catalyst was almost 4.8 times and 3 times of bulk photothermal catalysis and the relative bulk thermal catalysis. Experimental results proved that this excellent catalytic performance could be attributed to both the high temperature achieved and the enhanced lattice oxygen activity by solar irradiation. This IPC system also exhibited good universality and long-term durability. Our work innovatively created a green strategy to obtain fine chemicals with only solar irradiation.
Ni-loaded CeO2-based materials are one type of the promising catalyst for CO2 methanation; however, lowering the Ni loading, simplifying the preparation process of CeO2 supports, and improving the low-temperature catalytic performance are always essential for scalable applications. Herein, an efficient CeO2 support (CeO2-NC) with a large inner pore size was prepared by a facilely controlled calcination of cerium nitrate [Ce(NO3)3 center dot 6H2O] method. On the basis of CeO2-NC, one catalyst (Ni/CeO2-NC) with low Ni loading (2.56 wt %), desirable Ni dispersity, and abundant medium basic sites was developed that exhibited the amazing low-temperature CO2 methanation performance. At 275 degrees C, CO2 conversion reached up to 77.7% with an almost 100% CH4 selectivity under a high gas hourly space velocity of 60000 mL gcat-1 h-1, and the Ni-based mass-specific CH4 formation rate at 300 degrees C was up to 4740 mu mol gNi-1 s-1, outperforming most of the reported Ni-based catalysts to date. The in situ diffuse-reflectance infrared Fourier transform spectroscopy experiments revealed that plentiful active bidentate carbonate intermediates and effective suppression of the dissociated active H species recombination contributed to the boosted CO2 methanation performance of Ni/CeO2-NC at low temperatures. Moreover, the mechanism was also inferred. This work provides new insight into simple pyrolysis CeO2 supports and should be of significance for the rational design of highly efficient CO2 methanation catalysts.
For tandem reactions with several intermediate products, improving the reaction rate of each step is vital for accelerating the entire reaction. However, simultaneously enhancing the conversions of different intermediates using a single-active-site catalyst remains a challenge because the catalyst commonly promotes only one type of reaction. Herein, a Co-based double-active-site relay catalyst (denoted as (Co-1 -> Co-p)/N-CNTs) is reported. Due to the preferable catalytic activities of Co single atoms (Co-1) and Co nanoparticles (Co-p) for the oxidation of hydroxyls to aldehyde groups and aldehydes to carboxyl groups, respectively, the prepared (Co-1 -> Co-p)/N-CNTs exhibited good catalytic performance for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The catalyst achieved 100% HMF conversion efficiency and 96% FDCA yield under a 0.1 MPa O-2 atmosphere at 100 degrees C for 8 h. The presented strategy offers prospects for the development of highly active catalysts for complex tandem reactions.
The catalytic hydrogen transfer (CHT) cascade reaction between alcohols and nitro- compounds meets green chemistry yet involves high catalyst requirements. Herein, a hierarchical nano-pyramid structure, in which cobalt single atoms (Co SAs) are deposited on highly dispersed ZnO nanoparticles supported by nitrogen-doped carbon (denoted as Co-ZnO/NC), was designed and obtained through pyrolysis of ZnCo-ZIF. The catalyst exhibited excellent catalytic performance toward the CHT cascade reaction, achieving a high nitrobenzene conversion (94 %), imine selectivity (97 %), and turnover frequency (8.8 h-1). This nano-pyramid is a state-ofthe-art non-noble-metal catalyst and is comparable to noble-metal catalysts. Experimental and DFT results revealed that the Co SAs supported on ZnO reduced the reaction energy barrier of hydroxyl dehydrogenation, the first and rate-determining step in this heterogeneous catalysis. Furthermore, Co-ZnO/NC exhibits good recyclability and universality. Our findings offer a new catalyst for Schiff base synthesis and aid understanding of the roles of Zn in ZIF-derived carbon catalysts.
Primary amine self-coupling is of significant importance in imine synthesis,yet the thermal catalysis of amine self-coupling normally requires a high temperature or theaddition of expensive oxidants. Herein, Ce-doped MnOxcatalysts were prepared by threedifferent methods, and their surface properties were thoroughly characterized. The Ce-doped MnOxcatalyst obtained by redox-precipitation (CeMn-RO) showed efficientcatalytic performance toward imine synthesis from benzylamine oxidation under mildconditions (80 degrees C, 8 h, air balloon), achieving high benzylamine conversion (92%). Theexceptional oxidative ability of this catalyst could be attributed to its high concentration ofsurface Ce3+,Mn3+, and oxygen vacancies, facilitating the formation of surface oxygenspecies that play a vital role in the reaction. Furthermore, DRIFTS studies were carried outunder the reaction conditions, offering powerful evidence of the benzylamine oxidationmechanism over CeMn-RO
The intrinsic sluggish kinetics of the oxygen evolution reaction (OER) limit the improvement of hydrogen evolution reaction (HER) performance, and substituting the anodic oxidation of biomass materials is an alternative approach, given its lower oxidation potential and higher added value compared to those of OER. In this study, a Ni3S2-MoS2 nanoheterojunction catalyst with strong electronic interactions is prepared. It exhibits high efficiency for both the HER and the electrooxidation of 5-hydroxymethylfurfural (HMF). In a two-electrode cell with Ni3S2-MoS2 serving as both the anode and cathode, the potential is only 1.44 V at a current density of 10 mA cm(-2), which is much lower than that of pure water splitting. Density functional theory calculations confirm that the strong chemisorption of H and HMF at the interface leads to outstanding electrocatalytic activity. The findings not only provide a strategy for developing efficient electrocatalysts, but also provide an approach for the continuous production of high value-added products and H-2.
Quick fever screening at a mass scale is proven effective during a pandemic to single out the ones with suspected symptoms of infectious diseases. However, achieving affordable and real-time fever alert at an individual level, although more preferable, remains elusive. Herein, we report an inexpensive and highly sensitive fever detector, which possesses a sharp color transition temperature window tailor-tuned for fever screening. The sensing component of the detector is rationally designed thermoresponsive agarose@poly(N-isopropylacrylamide)-co-acrylamide hydrogel. The hydrogel turns from transparent to opaque white when its temperature is higher than its cloud point. As a proof of concept of its practical applicability, a wearable fever monitoring device was fabricated in the form of a wristband. When the wrist temperature is higher than the threshold of a human fever, the device shows a remarkable color change, alerting an elevated body temperature. The wearable detector provides a promising strategy for real-time fever alert monitoring and is capable of making contributions to inhibit the spread of infectious diseases during a pandemic.
Rapid self-healing of micro-configurations is an effective strategy to enhance the durability of superhydrophobic surfaces, however, this property is challenging to achieve. Here, a durable superhydrophobic coating with a precisely targeted self-healing ability to repair its' dual structure was developed by spray-coating a polyimine film with a mixture of novel fluorinated epoxy resin and Fe3O4@SiO2-NH2 nanoparticles. The superhydrophobic surface can heal both the broken morphology and wettability through a short irradiation process on account of its local photothermal conversion ability and dynamic imine bond, and can maintain the static water contact angle at a value higher than 159 degrees even after six damage/healing cycles. Furthermore, superhydrophobic coatings can be controllably degraded in three ways. Additionally, because of the robust epoxy resin protection, the surface can withstand sixteen times the dynamic impact and still maintain a WCA greater than 150 degrees. This preparation strategy may aid the fabrication of durable superhydrophobic surfaces for various practical applications.
Summary of main observation and conclusionThe pursuit of modern sustainable chemistry has stimulated the development of innovative catalytic processes that enable chemical transformations to be performed under mild and clean conditions with high efficiency. Here, an amorphous sheet‐like MnO2 (Ce‐doped MnO2: CMBO) was obtained after Ce doping, which exhibits excellent catalytic performance for the oxidation coupling of alcohol and aniline. Conversion of 99% and a selectivity of 99% could be achieved within 6 h at 60 oC under air atmosphere, and the formation rate of target product was up to 30.2 μmol·h–1·m–2. Based on a series of characterizations, it was found that the doping of Ce into the MnO2 could increase the concentration of the oxygen vacancies, thus forming abundant active surface oxygen species and favoring the mobility of lattice oxygen, which are the main reasons for the greatly enhanced catalytic performance of CMBO. This work indicates that increasing oxygen vacancy by element doping may serve as a facile and efficient way to enhance catalytic performance of transition metal oxide.
Developing heterogeneous catalysts for hydrogenation under mild conditions is industrially significant, but there still remain some challenges in the preparation of inexpensive and highly active catalysts. Herein, we present Co-MoxC catalysts prepared by a one-pot pyrolysis method for which excellent catalytic performance toward selective hydrogenation is achieved. The highest turnover frequency (TOF) of nitrobenzene hydrogenation reached up to 105.3 h(-1) with a selectivity of higher than 99% at 60 degrees C. As evidenced by our experiment and analysis, the electronic structure of cobalt can be affected by the in situ-formed molybdenum carbide, which led to an improved dispersion via the interaction between Co and MoxC as well as advanced catalytic performance. These results could provide some potential for the design of efficient hydrogenation catalysts for further industrial applications.
•Cobalt embedded into N-doped carbon was fabricated through one-pot pyrolysis of a mixture of Co (Ⅱ)-tannic acid coordination polymers and melamine.•The dosage of tannin acid in catalyst preparation process was a crucial factor in affecting the dispersion and exposure degree of Co nanoparticles.•The Co@CN catalyst exhibited an excellent catalytic performance for the liquid-phase hydrogenation of halogenated nitrobenzenes under 1 MPa H2 at 60 °C.
Functional silica microparticle is a kind of important inorganic non-metallic oxide with a wide range of applications in many fields due to its excellent chemical and thermal stabilities. Post modification is the most common functional method, but, low efficiency. In this paper, a new acid hydrolysis and subsequent alkaline condensation method was developed to prepare SiO 2 microspheres with functional groups on surface by condensing or co-condensing functional organosilane precursors (γ-Aminopropyltriethoxysilane (APTES), γ-Mercaptopropyltriethoxysilane (MPTES) and γ-Mercaptopropyltrimethoxysilane (MPTMS) etc) with phenyltrimethoxysilane (PTMS). Series of characterization methods, such as IR, XPS and Raman, demonstrated that the surface of the as-prepared SiO 2 microspheres was successfully functionalized with amine or sulfydryl groups. This method may provide a reference for one-step preparation of functional SiO 2 microspheres.
Monodisperse poly(glycidyl methacrylate)/polystyrene (PGMA/PS) anisotropic microspheres have been fabricated by seed polymerization. From the SEM images, it is known that the obtained PGMA/PS microspheres have three different morphologies: raspberry-shaped, golf-shaped and porous structures. Based on the successful fabrication of these micropheres, bovine serum albumin (BSA)-imprinted PGMA/PS microspheres were fabricated via dopamine auto-polymerization in alkaline solution. Because dopamine does not affect the validity of the protein structure, the imprinted cavity structure on the surface of the MIPs can match the template protein molecules completely. The obtained micron-sized BSA-imprinted PGMA/PS microspheres have an excellent saturation adsorption capacity (Q = 72.7 mg g-1) and good selective adsorption for BSA (IF = 4.6).
Five different nanocerias were prepared and used to catalyze the direct coupling of alcohol and amine to the corresponding imines under air atmosphere at low temperature. The catalytic efficiencies have great differences, CeO2 prepared by coprecipitation at room temperature (called CeO2-5) has the best catalytic activity, whose yield reaches 99% at 303 K for 36 h, 100 times higher than the nano-octahedras ceria (called CeO2-4) and also higher than the catalytic performance of most reported catalysts. Such phenomena are ascribed to the higher acidic sites, specific surface area, and proportions of surface oxygen. The results of DRIFTS demonstrated that the alcohol oxidized to benzaldehyde was the rate determining step in this reaction. Furthermore, CeO2-5 still shows excellent catalytic performance on 10-fold magnification experiments without any addition of solvent. Besides, it has the advantages of simple process, low energy consumption and practical scaling-up as well as good universality towards this kind of reaction, showing every prospect in industrial application.
Different crystal planes of CeO2 have a different number of broken bonds, surface energy and catalytic activities, so preparing the CeO2 with different exposed planes has attracted extensive attention. In recent years, the preparation of CeO2 nanocubes with {100} exposed plane has been a real hotspot of research because of its good catalytic performance. Based on the research about the alkali concentration, reaction temperature and reaction time, the formation mechanism of CeO2 nanocubes was explored. It is believed that the dissolution-recrystallization process is accelerated in the condition of strong base, high temperature and high pressure. In other word, the Ostwald ripening process is strengthened, which is the decisive factor for the formation of CeO2 nanocubes.
The redox properties of different crystal structure MnO2 in organic reactions at low temperature of 60 degrees C were disclosed. Among the three crystal structures (alpha-, beta- and y-types), gamma-MnO2 showed unusual high heterogeneous catalytic performance, reusability and stability for imine formation from benzyl alcohol and aniline under mild conditions. The yield of imine over gamma-MnO2 reached up to 98.1% in 12 h under air atmosphere and its formation rate per surface area was 27.9 mu mol h(-1) m(-2), and various imines could be obtained in excellent yield over gamma-MnO2. Based on series of catalyst characterizations, it was found that the high activity of gamma-MnO2 was mainly attributed to its high concentration of low-valence manganese ions. Furthermore, the catalytic mechanism was also disclosed. This research may have certain reference value for heterogeneous catalytic reactions by manganese.
Nanocomposites are fabricated with poly (glycidyl methacrylate) (PGMA) microspheres, Au nanoparticles and hyaluronic acid (HA) for accurate photothermal therapy. PGMA microspheres are synthesized by emulsifier-free emulsion polymerization followed by amination. The adsorption of gold seeds is successfully achieved through chelation. PGMA@Au-4 nanocomposites (abbreviated as PGMA@Au) are obtained after gold seed growth. The temperature of the 0.3 mg mL−1 PGMA@Au dispersion increases by 10.6 °C when irradiated with a near-infrared (NIR) laser for 5 min. In order to reduce side effects in normal cells and achieve a specific targeting property for cancer cells, HA is further conjugated on the surface of PGMA@Au (denoted as PGMA@Au–HA). The PGMA@Au–HA nanocomposites perform highly selective targeting toward cancer cells and have good photothermal properties, leading to threefold therapeutic efficacy against cancer cells in comparison with normal cells. These results indicate that the PGMA@Au–HA construct could be a promising platform for cancer therapy.