From the {FeIII2Ln2} Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d–4 f Based Coordination Clusters

In this Review we discuss the tuning handles which can be used to steer the magnetic properties of Fe^III-4 f “butterfly” compounds. The majority of presented compounds were produced in the context of project A3 “Di- to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions” within the SFB/TRR88 “3MET”. These contain {Fe^III₂Ln₂} cores encapsulated in ligand shells which are easy to tune in a “test-bed” system. We identify the following advantages and variables in such systems: (i) the complexes are structurally simple usually with one crystallographically independent Fe^III and Ln^III, respectively. This simplifies theory and anaylsis; (ii) choosing Fe allows ⁵⁷Fe Mössbauer spectroscopy to be used as an additional technique which can give information about oxidation levels and spin states, local moments at the iron nuclei and spin-relaxation and, more importantly, about the anisotropy not only of the studied isotope, but also of elements interacting with this isotope; (iii) isostructural analogues with all the available (i. e. not Pm) 4 f ions can be synthesised, enabling a systematic survey of the influence of the 4 f ion on the electronic structure; (iv) this cluster type is obtained by reacting [Fe^III₃O(O₂CR)₆(L)₃](X) (X=anion, L=solvent such as H₂O, py) with an ethanolamine-based ligand L′ and lanthanide salts. This allows to study analogues of [Fe^III₂Ln₂(μ₃-OH)₂(L′)₂(O₂CR)₆] using the appropriate iron trinuclear starting materials. (v) the organic main ligand can be readily functionalised, facilitating a systematic investigation of the effect of organic substituents on the ligands on the magnetic properties of the complexes. We describe and discuss 34 {M^III₂Ln₂} (M=Fe or in one case Al) butterfly compounds which have been reported up to 2020. The analysis of these gives perspectives for designing new SMM systems with specific electronic and magnetic signatures     

Palladium‐catalyzed Suzuki–Miyaura coupling with aryl and heteroaryl bromides using N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine

An easily prepared tetraphosphine N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine (1) combined with PdCl₂ affords an efficient catalytic system for Suzuki cross‐coupling of aryl and heteroaryl bromides. A high turnover number of 750 000 is obtained with the catalyst loading as low as 1 ppm. This catalyst system exhibits good stability and longevity. In this study, a broad scope of substrates is investigated and satisfactory yields are obtained. Copyright © 2012 John Wiley & Sons, Ltd.     

Synergistic Effect of Boron Nitride and Carbon Domains in Boron Carbide Nitride Nanotube Supported Single-Atom Catalysts for Efficient Nitrogen Fixation

Developing the low-cost and efficient single-atom catalysts (SACs) for nitrogen reduction reaction (NRR) is of great importance while remains as a great challenge. The catalytic activity, selectivity and durability are all fundamentally related to the elaborate coordination environment of SACs. Using first-principles calculations, we investigated the SACs with single transition metal (TM) atom supported on defective boron carbide nitride nanotubes (BCNTs) as NRR electrocatalysts. Our results suggest that boron-vacancy defects on BCNTs can strongly immobilize TM atoms with large enough binding energy and high thermal/structural stability. Importantly, the synergistic effect of boron nitride (BN) and carbon domains comes up with the modifications of the charge polarization of single-TM-atom active site and the electronic properties of material, which has been proven to be the essential key to promote N₂ adsorption, activation, and reduction. Specifically, six SACs (namely V, Mn, Fe, Mo, Ru, and W atoms embedded into defective BCNTs) can be used as promising candidates for NRR electrocatalysts as their NRR activity is higher than the state-of-the art Ru(0001) catalyst. In particular, single Mo atom supported on defective BCNTs with large tube diameter possesses the highest NRR activity while suppressing the competitive hydrogen evolution reaction, with a low limiting potential of −0.62 V via associative distal path. This work suggests new opportunities for driving NH₃ production by carbon-based single-atom electrocatalysts under ambient conditions.     

不同尺寸的NdFeB稀土永磁体热退磁行为研究

针对不同类型及不同尺寸的两类NdFeB永磁体分别研究了它们随温度变化的热退磁行为。采用样品的整体剩余磁通来表征热退磁过程中磁体性能的变化。结果表明,Pc较小的永磁体温度稳定性较差,随温度的升高,样品的剩余磁通迅速衰减;Pc<<0.1的普通型永磁体,温度为100℃时样品的剩余磁通损失超过60%。高矫顽力型永磁体比普通型磁体具有更优越的温度稳定性和高温性能。温度升高主要导致磁体矫顽力降低,140℃时普通型磁体的矫顽力降低约80%,而高矫顽力型磁体的矫顽力只降低了约20%。     

Pd‐catalyzed homocoupling of arylhydrazines via C―N cleavage under O2

An efficient and simple synthetic method for biaryl synthesis was developed using Pd(OAc)₂ as catalyst from aryl hydrazides under O₂. Various biaryls were synthesized in good yields, offering an expedient protocol for the synthesis of symmetrical biaryl molecules via C―N cleavage. The reactions were performed in component solvent of toluene and acetone without using any pro‐oxidant. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of capacitance storage and cyclic voltammetry for the electrochemical oxidation of phenol on iridium and lead oxide electrodes

Journal of Solid State Electrochemistry - The capacitance storage and cyclic voltammetry (CV) of electrochemical oxidation of phenol were investigated using IrO2–Ta2O5/Ti and β-PbO2/Ti...