Interfacial Electronic Modulation of Dual-Monodispersed Pt-Ni3S2 as Efficacious Bi-Functional Electrocatalysts for Concurrent H2 Evolution and Methanol Selective Oxidation.

Constructing the efficacious and applicable bi-functional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction (OER) are critical to the development of electrochemically-driven technologies for efficient hydrogen production and avoid CO2 emission. Herein, the hetero-nanocrystals between monodispersed Pt (~ 2 nm) and Ni3S2 (~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H2 generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt-Ni3S2 could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH3OH to formate is accomplished at very low potentials (1.45 V) to attain 100 mA cm-2 with high electronic utilization rate (~ 98%) and without CO2 emission. Meanwhile, the Pt-Ni3S2 can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction (HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction (MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 mA cm-2 with good reusability.

High-Valent Ni and Cu Complexes of a Tetraanionic Bis(amidateanilido) Ligand.

High-valent metal species are often invoked as intermediates during enzymatic and synthetic catalytic cycles. Anionic donors are often required to stabilize such high-valent states by forming strong bonds with the Lewis acidic metal centers while decreasing their oxidation potentials. In this report, we discuss the synthesis of two high-valent metal complexes [ML]+ in which the NiIII and CuIII centers are ligated by a new tetradentate, tetraanionic bis(amidateanilido) ligand. [ML]+, obtained via chemical oxidation of ML, exhibits UV-vis-NIR, EPR, and XANES spectra characteristic of square planar, high-valent MIII species, suggesting the locus of oxidation for both [ML]+ is predominantly metal-based. This is supported by theoretical analyses, which also support the observed visible transitions as ligand-to-metal charge transfer transitions characteristic of square planar, high-valent MIII species. Notably, [ML]+ can also be obtained via O2 oxidation of ML due to its remarkably negative oxidation potentials (CuL/[CuL]+: -1.16 V, NiL/[NiL]+: -1.01 V vs Fc/Fc+ in MeCN). This demonstrates the exceptionally strong donating nature of the tetraanionic bis(amidateanilido) ligation and its ability to stabilize high-valent metal centers..

Mechanisms of orthophosphate removal from water by lanthanum carbonate and other lanthanum-containing materials.

Removing phosphorus (P) from water and wastewater is essential for preventing eutrophication and protecting environmental quality. Lanthanum [La(III)]-containing materials can effectively and selectively remove orthophosphate (PO4) from aqueous systems, but there remains a need to better understand the underlying mechanism of PO4 removal. Our objectives were to 1) identify the mechanism of PO4 removal by La-containing materials and 2) evaluate the ability of a new material, La2(CO3)3(s), to remove PO4 from different aqueous matrices, including municipal wastewater. We determined the dominant mechanism of PO4 removal by comparing geochemical simulations with equilibrium data from batch experiments and analyzing reaction products by X-ray diffraction and scanning transmission electron microscopy with energy dispersive spectroscopy. Geochemical simulations of aqueous systems containing PO4 and La-containing materials predicted that PO4 removal occurs via precipitation of poorly soluble LaPO4(s). Results from batch experiments agreed with those obtained from geochemical simulations, and mineralogical characterization of the reaction products were consistent with PO4 removal occurring primarily by precipitation of LaPO4(s). Between pH 1.5 and 12.9, La2(CO3)3(s) selectively removed PO4 over other anions from different aqueous matrices, including treated wastewater. However, the rate of PO4 removal decreased with increasing solution pH. In comparison to other solids, such as La(OH)3(s), La2(CO3)3(s) exhibits a relatively low solubility, particularly under slightly acidic conditions. Consequently, release of La3+ into the environment can be minimized when La2(CO3)3(s) is deployed for PO4 sequestration.

Effects of Bi(Zn2/3Nb1/3)O3 Modification on the Relaxor Behavior and Piezoelectricity of Pb(Mg1/3Nb2/3)O3-PbTiO3 Ceramics.

Relaxor lead magnesium niobate (PMN)-based materials exhibit complex structures and unusual properties that have been puzzling researchers for decades. In this paper, a new ternary solid solution of Pb(Mg1/3Nb2/3)O3-PbTiO3-Bi(Zn2/3Nb1/3)O3 (PMN-PT-BZN) is prepared in the form of ceramics, and the effects of the incorporation of BZN into the PMN-PT binary system are investigated. The crystal structure favors a pseudocubic symmetry and the relaxor properties are enhanced as the concentration of BZN increases. The relaxor behavior and the related phase transformations are studied by dielectric spectroscopy. A phase diagram mapping out the characteristic temperatures and various states is established. Interestingly, the piezoelectricity of the PMN-PT ceramics is significantly enhanced by the BZN substitution, with an optimal value of d33 reaching 826 pC/N for 0.96[0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3]-0.04Bi(Zn2/3Nb1/3)O3. This paper provides a better understanding of the relaxor ferroelectric behavior, and unveils a new relaxor-based ternary system as piezoelectric materials potentially useful for electromechanical transducer applications.

Non-innocent ligand behavior of a bimetallic Ni Schiff-base complex containing a bridging catecholate.

The geometric and electronic structure of a bimetallic Ni Schiff-base complex and its one-electron oxidized form have been investigated in the solid state and in solution. The two salen units in the neutral complex 1 are linked via a bridging catecholate function. The one-electron oxidized form [1](+) was determined to exist as a ligand radical species in solution, with the electron hole potentially localized on the redox-active dioxolene, the phenolate ligands, or delocalized over the entire ligand system. Electrochemical experiments and UV-vis-NIR spectroscopy, in combination with density functional theory (DFT) calculations, provide insight into the locus of oxidation and the degree of delocalization in this system. The one-electron hole for [1](+) was determined experimentally to be localized on the dioxolene bridge with a small amount of spin density on the outer phenolate moieties predicted by the calculations. The resonance Raman spectrum of [1](+) (λ(ex) = 413 nm) in CH(2)Cl(2) solution clearly exhibited a new band at 1315 cm(-1) in comparison to 1, which is predicted to be a combination of dioxolene ring and C-O bond stretching modes, consistent with oxidation of the bridging moiety in [1](+). Analysis of the NIR bands for [1](+), in association with time-dependent DFT calculations, suggests that the low energy bands are ligand to ligand charge transfer transitions from the terminal phenolates to the central dioxolene unit. In combination, this data is consistent with a description of the overall electronic structure of [1](+) as a bridge-localized semiquinone ligand radical species. This is in contrast to the mixed-valence ground state description for many one-electron oxidized Ni salen monomer systems, and analysis in terms of intervalence charge transfer (IVCT) theory.