Synergistically Coupled Ni/CeOx@C Electrocatalysts for the Hydrogen Evolution Reaction: Remarkable Performance to Pt/C at High Current Density.

Incredibly active electrocatalysts comprising earth-abundant materials that operate as effectively as noble metal catalysts are essential for the sustainable generation of hydrogen through water splitting. However, the vast majority of active catalysts are produced via complicated synthetic processes, making scale-up considerably tricky. In this work, a facile strategy is developed to synthesize superhydrophilic Ni/CeOx nanoparticles (NPs) integrated into porous carbon (Ni/CeOx@C) by a simple two-step synthesis strategy as efficient hydrogen evolution reaction (HER) electrocatalysts in 1.0 M KOH. Benefiting from the electron transport induced by the heterogeneous interface between Ni and CeOx NPs and the superhydrophilic structure of the catalyst, the resultant Ni2Ce1@C/500 catalysts exhibit a low overpotential of 26 and 184 mV at a current density of 10 and 300 mA cm-2, respectively, for HER with a small Tafel slope of 62.03 mV dec-1 and robust durability over 300 h, and its overpotential at a high current density is much better than the benchmark commercial Pt/C. Results revealed that the electronic rearrangement between Ni and CeOx integrated into porous carbon could effectively regulate the local conductivity and charge density. In addition, the oxygen vacancies and Ni/CeOx heterointerface promote water adsorption and hydrogen intermediate dissociation into H2 molecules, which ultimately accelerate the HER reaction kinetics. Notably, the electrochemical results demonstrate that structural optimization by regulating synthesis temperature and metal concentration could improve the surface features contributing to high electrical conductivity and increase the number of electrochemically active sites on the Ni/CeOx@C heterointerface, high crystal purity, and better electrical conductivity, resulting in its exceptional electrocatalytic performance toward the HER. These results indicated that the Ni/CeOx@C electrocatalyst has the potential for practical water-splitting applications because of its controlled production strategy and outstanding Pt-like HER performance.

Synthesis of Isoindolinones by Pd-Catalyzed Coupling between N-Methoxybenzamide and Styrene Derivatives.

An atom-economical protocol for a tandem process involving Fujiwara-Moritani-aza-Wacker reactions has been developed for the Pd-catalyzed coupling between N-methoxy benzamide and styrene derivatives. The generality of the methodology was demonstrated by the synthesis of a library of 25 3-benzylidene isoindolinones in moderate to good yields. A further 40 3-benzyl derivatives were obtained by telescoping the process with a catalytic hydrogenation reaction.

Quercetin-Iron Complex: Synthesis, Characterization, Antioxidant, DNA Binding, DNA Cleavage, and Antibacterial Activity Studies.

Quercetin-iron (II) complex was synthesized and characterized by elemental analysis, ultraviolet-visible spectrophotometry, fourier transform infrared spectroscopy, mass spectrometry, proton nuclear magnetic resonance spectroscopy, thermogravimetry and differential scanning calorimetry, scanning electron micrography and molar conductivity. The low molar conductivity value investigates the non-electrolyte nature of the complex. The elemental analysis and other physical and spectroscopic methods reveal the 1:2 stoichiometric ratio (metal:ligand) of the complex. Antioxidant study of the quercetin and its metal complex against 2, 2-di-phenyl-1-picryl hydrazyl radical showed that the complex has much more radical scavenging activity than free quercetin. The interaction of quercetin-iron (II) complex with DNA was determined using ultraviolet visible spectra, fluorescence spectra and agarose gel electrophoresis. The results showed that quercetin-iron (II) complex can intercalate moderately with DNA, quench a strong intercalator ethidium bromide and compete for the intercalative binding sites. The complex showed significant cleavage of pBR 322 DNA from supercoiled form to nicked circular form and these cleavage effects were dose-dependent. Moreover, the mechanism of DNA cleavage indicated that it was an oxidative cleavage pathway. These results revealed the potential nuclease activity of complex to cleave DNA. In addition, antibacterial activity of complex on E.coli and S. aureus was also investigated. The results showed that complex has higher antibacterial activity than ligand.

Three N-H functionalized metal-organic frameworks with selective CO2 uptake, dye capture, and catalysis.

Three N-H functionalized metal-organic frameworks, Pb-DDQ, Zn-DDQ, and Cu-DDQ, were synthesized with a new flexible dicarboxylate ligand based on quinoxaline (H2DDQ = N,N'-dibenzoic acid-2,3-diaminoquinoxaline). CO2 adsorptions indicate that Zn-DDQ and Cu-DDQ have greatly enhanced the CO2 uptake due to the opposite N-H groups on pyrazine. With very small adsorption of N2, Cu-DDQ shows high selectivity for CO2 and N2. The three MOFs also have large adsorptions of some selected dyes, while Zn-DDQ and Cu-DDQ with large but different shapes of pores are demonstrated to be promising materials for fast separation of MB/other and CV/other mixtures, respectively. The cyanosilylation of aldehydes and ketones with high yields in a short reaction time for Cu-DDQ indicates that Cu-DDQ has a higher Lewis acidity than the other two MOFs.

Multifunctional light-controllable nanozyme enabled bimodal fluorometric/colorimetric sensing of mercury ions at ambient pH.

Nanomaterials with enzyme-like catalytic features (nanozymes) find wide use in analytical sensing. Apart from catalytic characteristics, some other interesting functions coexist in the materials. How to combine these properties to design multifunctional nanozymes for new sensing strategy development is challenging. Besides, in nanozymes it is still a challenge to conveniently control the catalytic process, which also hinders their further applications in advanced biochemical analysis. To remove the above barriers, here we design a light-controllable multifunctional nanozyme, namely manganese-inserted cadmium telluride (Mn-CdTe) particles, that integrates oxidase-like activity with luminescence together, to achieve the fluorometric/colorimetric dual-mode detection of toxic mercury ions (Hg2+) at ambient pH. The Mn-CdTe exhibits a light-triggered oxidase-mimicking catalytic behavior to induce chromogenic reactions, thus enabling one to start or stop the catalytic progress easily via applying or withdrawing light irradiation. Meanwhile, the quantum dot material can exhibit bright photoluminescence, which provides the fluorometric channel to sense targets. When Hg2+ is introduced, it rapidly leans toward Mn-CdTe through electrostatic interaction and Te-Hg bonding and induces the aggregation of the latter. As a result, the luminescence of Mn-CdTe is dynamically quenched, and the masking of active sites in aggregated Mn-CdTe leads to the decrease of light-initiated oxidase-mimetic activity. According to this principle, a new fluorometric/colorimetric bimodal method was established for Hg2+ determination with excellent performance. A 3D-printed portable platform combining paper-based test strips and an App-equipped smartphone was further fabricated, making it possible to achieve in-field sensing of the analyte in various matrices.

Construction lamellar BaFe12O19/Bi3.64Mo0.36O6.55 photocatalyst for enhanced photocatalytic activity via a photo-Fenton-like Mo6+/Mo4+redox cycle.

The novel BaFe12O19/Bi3.64Mo0.36O6.55 composite materials were constructed as magnetically recyclable photo-Fenton-like degradation systems. The composite catalyst not only promoted the effective transfer of photo-generated electrons and improved the Mo6+/Mo4+ cycle consequent, but also activated hydrogen peroxide to generate oxidizing free radicals. BaFe12O19/Bi3.64Mo0.36O6.55-0.25 exhibited an outstanding degradation performance for tetracycline hydrochloride it is 1.3 times to Bi3.64Mo0.36O6.55. The thermal catalytic performance of the Bi3.64Mo0.36O6.55 monomer is similar to that of the BaFe12O19/Bi3.64Mo0.36O6.55 material without light. However, the removal rate of BaFe12O19/Bi3.64Mo0.36O6.55 material reaches 84.5% after 60 min with light, far exceeding that of Bi3.64Mo0.36O6.55 material. By way of the contrast experiment with light and without light, it is further demonstrated that interfacial interaction between BaFe12O19 and Bi3.64Mo0.36O6.55 acted a key role in the photocatalytic reaction system. It is also a good advantage that pollutants can be efficiently degraded without adjusting the pH. The characterization of photocurrent and X-ray photoelectron spectroscopy (XPS) also further proved the synergy between the two materials, which is useful to the separation of electrons and holes. The synergy ultimately improves the degradation performance. Besides, BaFe12O19/Bi3.64Mo0.36O6.55 can be easily separated by an external magnetic field after the photocatalytic activity reaction owing to BaFe12O19's magnetic properties. It provides a new research idea for the construction and iron-based heterogeneous Fenton-like system for magnetic degradation of antibiotics.

Rutin-Nickel Complex: Synthesis, Characterization, Antioxidant, DNA Binding, and DNA Cleavage Activities.

The rutin-nickel (II) complex (RN) was synthesized and characterized by elemental analysis, UV-visible spectroscopy, IR, mass spectrometry, 1H NMR, TG-DSC, SEM, and molar conductivity. The low molar conductivity value investigates the non-electrolyte nature of the complex. The elemental analysis and other physical and spectroscopic methods reveal the 1:2 stoichiometric ratio (metal/ligand) of the complex. An antioxidant study of rutin and its metal complex against DPPH radical showed that the complex has more radical scavenging activity than free rutin. The interaction of complex RN with DNA was determined using fluorescence spectra and agarose gel electrophoresis. The results showed that RN can intercalate moderately with DNA, quench a strong intercalator ethidium bromide (EB), and compete for the intercalative binding sites. The complex showed significant cleavage of pBR 322 DNA from supercoiled form (SC) to nicked circular form (NC), and these cleavage effects were dose-dependent. Moreover, the mechanism of DNA cleavage indicated that it was a hydrolytic cleavage pathway. These results revealed the potential nuclease activity of the complex to cleave DNA.

Two chelating-amino-functionalized lanthanide metal-organic frameworks for adsorption and catalysis.

Two chelating-amino-functionalized lanthanide metal-organic frameworks, Er-DADQ and Eu-DADQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H2DADQ = N,N'-dibenzoic acid-2,3-diaminoquinoxaline). N2 adsorption indicates that they exhibit a stable microporous framework with a BET surface area of 136.78 m(2) g(-1). CO2 adsorptions have also been studied at different temperatures. The amino groups in the MOFs enhanced the uptake of RhB with COOH groups. RhB-MO and RhB-CV separations have also been successfully conducted. The MOFs act as efficient Lewis acid catalysts for the cyanosilylation of aldehydes and ketones in high yields in a short reaction time due to the higher Lewis acidity and open sites of the metal ions after activation.

Bis[2-(3-pyridinio)benzimidazolium] di-mu-chloro-bis[trichlorocadmium(II)].

The title compound, (C12H11N3)2[Cd2Cl8], consists of two discrete 2-(3-pyridinio)benzimidazolium cations and one [Cd2Cl8]4- anion. The dimeric [Cd2Cl8]4- anion lies about an inversion centre and consists of two distorted [CdCl5] trigonal bipyramids which share a common edge. The two Cd atoms are each coordinated by two mu-Cl atoms and three terminal Cl atoms, with a Cd...Cd separation of 3.9853 (6) A. The packing displays two-dimensional hydrogen-bonded sheets, which are further linked by C-H...Cl contacts and pi-pi stacking interactions to yield a three-dimensional network.