Stable Hierarchical Porous Heterostructure Ni2P/NC@CoNi2S4 Fabricated via the NiCo-LDH Template Strategy for High-Performance Supercapacitors.

Transition metal phosphide/sulfide (TMP/TMS) heterostructures are attractive supercapacitor electrode materials due to their rapid redox reaction kinetics. However, the limited active sites and weak interfacial interactions result in undesirable electrochemical performance. Herein, based on constructing the NiCo-LDH template on Ni-MOF-derived Ni2P/NC, Ni2P/NC@CoNi2S4 with a porous heterostructure is fabricated by sulfurizing the intermediate and is used for supercapacitors. The exposed Ni sites in the phosphating-obtained Ni2P/NC coordinate with OH- to in situ form an intimate-connected Ni2P/NC@NiCo-LDH, and the CoNi2S4 nanosheets retaining the original cross-linked structure of NiCo-LDH integrate the porous carbon skeleton of Ni2P/NC to yield a hierarchical pore structure with rich electroactive sites. The conducting carbon backbone and the intense electronic interactions at the interface accelerate electron transfer, and the hierarchical pores offer sufficient ion diffusion paths to accelerate redox reactions. These confer Ni2P/NC@CoNi2S4 with a high specific capacitance of 2499 F·g-1 at 1 A·g-1. The NiCo-LDH template producing a tight interfacial connection, significantly enhances the stability of the heterostructure, leading to a 91.89% capacitance retention after 10,000 cycles. Moreover, the fabricated Ni2P/NC@CoNi2S4//NC asymmetric supercapacitor exhibits an excellent energy density of 73.68 Wh kg-1 at a power density of 700 W kg-1, superior to most reported composites of TMPs or TMSs.

In Situ MOF-74-Pyrolysis-Generated Porous Carbon Supporting Spinel Cu0.15Co2.85O4/C Boosts Ammonium Perchlorate Accelerating Decomposition: Precise Cu Doping Modulating Oxygen Vacancy Concentration.

As one of the main components of solid propellant, ammonium perchlorate (AP) shows slow sluggish decomposition kinetics with unconcentrated heat release. To achieve efficient catalytical decomposition, it is a significant challenge to design reasonable catalyst structure and explore the interaction between catalyst and AP. Herein, a series of porous carbon supported spinel-typed homogeneous heterometallic composites CuxCo3-xO4/C via pyrolysis of MOF-74-Co doped Cu. On basis of precise electronic-structure-tuning through modulating Cu/Co ratio in MOF-74, Cu0.15Co2.85O4/C with 5% Cu-doping featuring oxygen vacancy concentration of 26.25% exhibits the decrease to 261.5 °C with heat release up to 1222.1 J g-1 (456.9 °C and 669.2 J g-1 for pure AP). The detail process of AP accelerated decomposition is approved by TG-DSC-FTIR-MS technique. Density functional theory calculation revealed that in the Cu0.15Co2.85O4/C, the distinctive ability for NH3 catalyzed oxidation assisted with absorption performance of active porous C boosts accelerating AP decomposition. The findings would provide an insight for perceiving and understanding AP catalytic decomposition.

Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiW9Co3@UiO-67-NH2 Deciding High Stability and Photocatalytic CO2 Reduction Performance.

Merging metal-organic frameworks (MOFs) and polyoxometalates (POMs) into heterogeneous heterojunction photocatalysts through in situ encapsulation is an effective approach to suppress the leachability of POMs and enhance their electron supply. The heterointerfacial connection in POMs@MOFs directly determines the performance of stability and charge separation, and the suited interaction between MOFs and POMs for POMs@MOFs heterojunctions photocatalyst is of vital importance. Here, a distinctive Keggin-type POM [(n-C4H9)N]10[SiW9Co3 (H2O)3O37]·17H2O (SiW9Co3) with near-total visible region absorption, narrow band gap of 2.23 eV, and powerful electron supply activity was prepared and tightly immobilized in the cavities of UiO-67-NH2 and UiO-68-NH2 to construct two Z-scheme heterojunctions SiW9Co3@UiO-67-NH2 and SiW9Co3@UiO-68-NH2, which were used for photocatalytic reduction of CO2 to CO. Their compositions, structures, and energy band features were fully characterized by a series of tests including XRD, FT-IR, SEM, XPS, UV-vis-DRS, UPS, and so forth. SiW9Co3@UiO-67-NH2 showed optimal photocatalytic performance with an excellent CO yield of 153.3 µmol-1·g-1·h-1 and a selectivity of 100%, which is 3.3-fold higher than that of SiW9Co3@UiO-68-NH2 and far superior to most reported POM-based heterojunctions. Comprehensive investigations with extensive photoelectric characterizations and microcalorimetric experiments demonstrated that the exceptional photocatalytic performances of SiW9Co3@UiO-67-NH2 could be attributed to the fact that (i) strong host-guest interactions were formed due to the well-matched dimensions between SiW9Co3 cluster and MOF cavity, which generated an intimate heterointerface to effectively accelerate interface electron transfer; (ii) the intimate heterointerface promoted SiW9Co3 to yield multielectron supply for efficient interfacial carrier neutralization owing to its donor-acceptor structure and narrow band gap. Additionally, the excellent durability of SiW9Co3@UiO-67-NH2 was also supported by the solidly locked SiW9Co3 and a stable MOF framework.

In situ growth of copper-based energetic complexes on GO and an MXene to synergistically promote the thermal decomposition of ammonium perchlorate.

In this work, using tri(5-aminotetrazolium)triazine (H3TATT) as an energetic ligand, two new energetic complexes (ECs), Cu(HTATT)(H2O)2 (EC-Cu1) and [Cu3(TATT)2(H2O)2]n (EC-Cu2), have been synthesized under hydrothermal conditions. Their crystal structures, thermal decomposition behaviors and specific heat capacities were determined respectively. In addition, two ECs were combined with GO (graphene oxide) and an MXene (Ti3C2TX) respectively by an in situ growth strategy to obtain four carbon nanomaterials/EC composites, which were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The effects of two ECs and four composites on the thermal decomposition of AP were studied by differential scanning calorimetry (DSC). Among them, the sample containing 8 wt% composite (GO/EC-Cu2) has the best promoting effect on AP, causing the high temperature decomposition peak to overlap with the low temperature decomposition peak of AP, reducing the decomposition peak temperature of AP from 443.6 °C to 308.9 °C, and the heat release is up to 4875 J g-1. Compared with ECs acting solely on AP, composite materials have stronger synergistic and promoting effects. This study provides a new example of the synthesis of carbon nanomaterial/EC composites and the improvement of the performance of AP-based solid propellants.

A Stable Triphenylamine-Based Zn(II)-MOF for Photocatalytic H2 Evolution and Photooxidative Carbon-Carbon Coupling Reaction.

Efficient charge transfer has always been a challenge in heterogeneous MOF-based photoredox catalysis due to the poor electrical conductivity of the MOF photocatalyst, the toilless electron-hole recombination, and the uncontrollable host-guest interactions. Herein, a propeller-like tris(3'-carboxybiphenyl)amine (H3TCBA) ligand was synthesized to fabricate a 3D Zn3O cluster-based Zn(II)-MOF photocatalyst, Zn3(TCBA)2(µ3-H2O)H2O (Zn-TCBA), which was applied to efficient photoreductive H2 evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of N-aryl-tetrahydroisoquinolines and nitromethane. In Zn-TCBA, the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes Zn-TCBA to exhibit a broad visible-light absorption with a maximum absorption edge of 480 nm but also causes special phenyl plane twists with dihedral angles of 27.8-45.8° through the coordination to Zn nodes. The semiconductor-like Zn clusters and the twisted TCBA3- antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render Zn-TCBA a good photocatalytic H2 evolution efficiency of 27.104 mmol·g-1·h-1 in the presence of [Co(bpy)3]Cl2 under visible-light illumination, surpassing many non-noble-metal MOF systems. Moreover, the positive enough excited-state potential of 2.03 V and the semiconductor-like characteristics of Zn-TCBA endow Zn-TCBA with double oxygen activation ability for photocatalytic oxidation of N-aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of Zn-TCBA and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.

Influence of lattice water molecules on the magnetization dynamics of binuclear dysprosium(III) compounds: insights from magnetic and ab initio calculations.

Lattice water effects on the structures and magnetic properties of single-molecule magnets (SMMs) have attracted considerable attention. Herein, we have successfully synthesized two centrosymmetric binuclear compounds [Dy2(2,3'-ppcad)2(C2H3O2)4(H2O)2] (1) and [Dy2(2,3'-ppcad)2(C2H3O2)4(H2O)2]·6H2O (2) (2,3'-Hppcad = N3-(2-pyrazinyl)-3-pyridinecarboxamidrazone) by elaborately varying the amount of the base (LiOH·H2O). Through isothermal titration calorimetry (ITC), the interactions between DyIII ions and 2,3'-Hppcad with different amounts of LiOH·H2O were monitored in real time. Magnetic studies reveal that two compounds exhibit the typical zero-field single-molecule magnet behavior with different energy barrier (Ueff) values of 103.43 K for 1 and 386.48 K for 2, wherein the SMM performance for 2 stands out among the reported nine-coordinated Dy2-SMMs systems with spherical capped square antiprism (C4v) geometries. To rationalize the observed difference in the magnetic properties of 1 and 2, ab initio calculations have been performed. The introduction of lattice water molecules leads to differences in the J values observed for 1 and 2. The stronger antiferromagnetic DyIII-DyIII couplings in 2 were presented and the fast quantum tunneling of magnetization was further suppressed, thereby achieving a higher Ueff value. This work provides an effective strategy to enhance the SMM performance, and combines with ab initio calculations to explain how lattice water molecules can affect the magnetic interactions of Dy2-SMMs.

Copper nanocluster-Ru(dcbpy)32+ as a cathodic ECL-RET probe combined with 3D bipedal DNA walker amplification for bioanalysis.

In this study, a cathodic intra-molecular electrochemiluminescence resonance energy transfer (ECL-RET) probe was exquisitely designed via the integration of an ECL donor (Cu NCs) with an acceptor (Ru(dcbpy)32+), and further employed the 3D bipedal DNA walker amplification strategy to monitor the platelet-derived growth factor BB (PDGF-BB). Specifically, blue emission Cu NCs with low consumption, biocompatibility and numerous resources, act as well-overlapped donors and significantly improve the ECL efficiency of Ru(dcbpy)32+. More impressively, the intra-molecular ECL-RET of Cu NC-Ru endowed a better and more stable ECL signal by reducing the electron-transfer distance and decreasing the energy loss. Furthermore, 3D bipedal DNA walker amplification was employed to efficiently convert the target PDGF-BB into numerous DNA strands, achieving sensitive target amplification. By virtue of such design, the constructed aptasensor exhibited a sensitive and selective assay for PDGF-BB with a detection range from 0.01 pM to 10 nM and a detection limit of 3.3 fM. The intramolecular ECL-RET and 3D bipedal DNA walker amplification strategy designed in this study will provide valuable insight into promising ultrasensitive ECL bioanalysis.

Effects of strong coordination bonds at the axial or equatorial positions on magnetic relaxation for pentagonal bipyramidal dysprosium(III) single-ion magnets.

Three pentagonal bipyramidal mononuclear Dy(III) complexes based on amino-substituted nitrophenol and tetradentate amide ligands of formulas [Dy(Hbpen)(OPhNO2NH2Cl)Cl2] (1), [Dy(Hbpen)(OPhNO2NH2)Cl2] (2) and [Dy(Hbpen)(OPhNO2NH2Cl)3] (3) (Hbpen = N,N'-bis(2-pyridylmethyl)-ethylenediamine, OPhNO2NH2Cl = 2-amino-6-chloro-4-nitrophenol, and OPhNO2NH2 = 2-amino-4-nitrophenol) were isolated. X-ray diffraction studies illustrate that complexes 1 and 2 with one strongly coordinating phenol ligand at their equatorial positions have a similar structure except for a slight difference in the chloride substituent of the phenol ligand. Complex 3 possesses the same equatorial coordination as 1 but its apical positions are occupied by two other phenol ligands. Magnetic studies show that 1 and 2 are zero-field single-ion magnets (SIMs), and 3 exhibits field-induced SIM behavior. Upon removing the chloride substituent groups from the phenol ligand, the effective energy barrier enhances from 233.7 K (1) to 362.7 K (2) under external dc fields. The stronger quantum tunneling of magnetization observed for 3 in comparison with 1 shows the destructive influence of a strong phenoxyl oxygen ligand field contributing to the transverse component on the magnetic properties. A comparison of complex 2 and the reported Dy(III) analogue [Dy(Hbpen)Cl(OPhBr2NO2)2] with two phenol ligands (2,6-dibromo-4-nitrophenol) in the axial direction leads to the conclusion that the magnetic anisotropy is strongly dependent on the Dy-Ophenoxyl bond lengths. The results provide direct information vital to understanding how the strong coordination environment at the axial or equatorial positions influences the SIM behavior.

Core-shell Au@PtAg modified TiO2-Ti3C2 heterostructure and target-triggered DNAzyme cascade amplification for photoelectrochemical detection of ochratoxin A.

Efficient charge separation and utilization are critical factors to obtain a high initial signal in photoelectrochemical (PEC) aptasensor. Reports demonstrate that constructing metal/semiconductor Schottky junction can effectively improve the charge separation efficiency. Herein, a photoelectrode Au@PtAg/TiO2-Ti3C2 Schottky junction is successfully synthesized. Specifically, the Schottky junction between core-shell Au@PtAg and TiO2-Ti3C2 facilitates the efficiency of photogenerated electron transfer and enables the transfer of photogenerated electrons from TiO2-Ti3C2 to Au@PtAg. Noteworthy, the core-shell Au@PtAg acts as a photoelectron receiver to capture and store electrons, which further facilitates the separation of photogenerated electron-hole pairs, resulting enhanced photocurrent generation without sacrificial agents. Moreover, through the Mg2+-dependent DNAzyme cascade amplification, the sensitivity of the PEC aptasensor is further improved. Hence, we report an ultrasensitive PEC aptasensor for ochratoxin A (OTA) assy based on Au@PtAg/TiO2-Ti3C2 Schottky junction and Mg2+-dependent DNAzyme cascade amplification. As a result, the established PEC aptasensor exhibits excellent photocurrent performance in the range of 5 fg mL-1-10 ng mL-1 with a detection limit as low as 1.73 fg mL-1, showing high sensitivity, selectivity as well as stability. This strategy provides a versatile and promising avenue for the development of high-performance PEC aptasensor.

Dynamic Metal-Iodide Bonds in a Tetracoordinated Cadmium-Based Metal-Organic Framework Boosting Efficient CO2 Cycloaddition under Solvent- and Cocatalyst-Free Conditions.

Due to the inherent thermodynamic stability and kinetic inertness of CO2, heterogeneous catalytic conversion of CO2 to cyclic carbonates often requires harsh operating conditions, high temperature and high pressure, and the addition of cocatalysts. Therefore, the development of efficient heterogeneous catalysts under cocatalyst-free and mild conditions for CO2 conversion has always been a challenge. Herein, an infrequent tetracoordinated Cd-MOF was synthesized and used to catalyze CO2 cycloaddition reactions efficiently without the addition of any cocatalyst, and its catalytic mechanism was systematically investigated through a series of experiments, including fluorescence analysis, X-ray photoelectron spectroscopy, microcalorimetry, and density functional theory (DFT) calculation. Cd-MOF features a 3D supermolecule structure with 1D 11.6 × 7.7 Å2 channels, and the abundant Lewis acid/base and I- sites located in the confined channel boost efficient CO2 conversion with a maximum yield of 98.2% and a turnover number value of 1080.11 at 60 °C and 0.5 MPa, far surpassing most pristine MOF-based catalytic systems. A combined experimental and DFT calculation demonstrates that the exposed Cd(II) Lewis acid sites rapidly participate in coordination to activate the epoxides, and the resulting large steric hindrance facilitates leaving of the coordinated iodide ions in a reversibly dynamic fashion convenient for the rate-determining step ring-opening as a strong nucleophile. Such a pristine MOF catalyst with self-independent catalytic ring-opening overcomes the complicated operation limitation of the traditional cocatalyst-free MOF systems based on encapsulating/postmodifying cocatalysts, providing a whole new strategy for the development of simple, green, and efficient heterogeneous catalysts for CO2 cycloaddition.

Solvent-Free Lithium/Sodium-Based Metal-Organic Frameworks with Versatile Nitrogen-Rich Ligands: Insight for the Design of Promising Superheat-Resistant Explosives.

Energetic metal-organic frameworks (EMOFs) are very promising as heat-resistant explosives, affording both thermal stability and energy properties. In this work, the self-assembly of high-energy nitrogen-rich linkers with nontoxic alkali-metal lithium/sodium leads to four new solvent-free EMOFs. Because of unparalleled decomposition temperature (Tdec = 403 °C) and heats of detonation (3.475 kcal·g-1), a 3D Li(I)-EMOF can be considered to be a superheat-resistant explosive candidate.

Anionic oxoborane and thioxoborane molecules supported by a 1,2-bis(imino)acenaphthene ligand.

The isolable anionic oxoborane 3 and thioxoborane 4 have been assembled using a 1,2-bis(imino)acenaphthene ligand (Dip-BIAN). Structural characterization and DFT calculations confirmed that two compounds contain terminal doubly bonded B[double bond, length as m-dash]E (E = O, S) groups, respectively, in which only the B[double bond, length as m-dash]O group is associated with imidazolium via a hydrogen bond.

Tailoring Electronic Structure and Size of Ultrastable Metalated Metal-Organic Frameworks with Enhanced Electroconductivity for High-Performance Supercapacitors.

Utilization of metal-organic frameworks (MOFs) as electrodes for energy storage/conversion is challenging because of the low chemical stability and poor electrical conductivity of MOFs in electrolytes. A nanoscale MOF, Co0.24 Ni0.76 -bpa-200, possessing ultrahigh stability with uncommon semiconductor behavior (σ=4.2×10-3  S m-1 ) was fabricated. The MOF comprises a robust hydrophobic paddlewheel and an optimized Co/Ni ratio, with consequent control over MOF size and the degree of conjugation of the coligand. A DFT study revealed that appropriate Ni2+ doping reduces the activation energy of the system, thus providing a higher carrier concentration, and the strongly delocalized N-donor ligand notably increases the metal-ligand orbital overlap to achieve efficient charge migration, leading to continuous through-bond (-CoNi-N-CoNi-)∞ conduction paths. These structural features endow the MOF with a good cycling stability of 86.5 % (10 000 cycles) and a high specific capacitance of 1927.14 F g-1 among pristine MOF-based electrodes.

In Situ Ligand Formation in the Synthetic Processes from Mononuclear Dy(III) Compounds to Binuclear Dy(III) Compounds: Synthesis, Structure, Magnetic Behavior, and Theoretical Analysis.

Guided by the self-assembled process and mechanism, the strategy of in situ Schiff base reaction would be capable of bringing a feasible method to construct and synthesize lanthanide compounds with distinct structures and magnetic properties. A mononuclear Dy(III) compound was synthesized through a multidentate Schiff base ligand and a chelating ß-diketonate ligand, which was named as [Dy(L)(bppd)]·CH3OH [1; H2L = N,N'-bis(2-hydroxy-5-methyl-3-formylbenzyl)-N,N'-bis(pyridin-2-ylmethyl)ethylenediamine and bppd = 3-bis(pyridin-2-yl)propane-1,3-dione]. Furthermore, a new binuclear Dy(III) compound, [Dy2(H2Lox)(bppd)3]·8CH3OH [2; H4Lox = N,N'-bis[2-hydroxy-5-methyl-3-(hydroxyiminomethyl)benzyl]-N,N'-bis(pyridin-2-ylmethyl)ethylenediamine], was obtained via an in situ synthetic process. Under similar synthetic conditions, [Dy(L)(ctbd)] [3; ctbd = 1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedione] and [Dy2(H2Lox)(ctbd)3]·CH3OH·C4H10O (4) were synthesized by modifying the ß-diketonate ligand and in situ Schiff base reaction. Compound 3 is a mononuclear configuration, while compound 4 exhibits a binuclear Dy(III) unit. Therein, formylbenzyl groups of H2L in 1 and 3 were changed to (hydroxyiminomethyl)benzyl groups in 2 and 4, respectively. In isomorphous 2 and 4, two Dy(III) centers are connected through two phenol O- atoms of the H2Lox2- ligand to form a binuclear structure. Eight-coordinated Dy(III) ions with different distortions can be observed in 1-4. The crystals of 1 and 3 suffered dissolution/precipitation to obtain 2 and 4, respectively. The relationship between the structure and magnetism in compounds 1-4 was discussed through the combination of structural, experimental, and theoretical investigations. Especially, the rates of quantum tunneling of magnetization of 1-4 were theoretically predicted and are consistent with the experimental results. For 2 and 4, the theoretically calculated dipolar parameters Jdip are consistent with the experimental observation of weak ferromagnetic coupling.

Solvent responses and substituent effects upon magnetic properties of mononuclear DyIII compounds.

Solvent responsive magnets comprise a class of molecule-based materials where lattice solvent driven structural transformation leads to the switching of magnetic properties. Herein, we present a special type of magnet where single-crystal to single-crystal (SCSC) transformations within mononuclear DyIII compounds result in the switching of DyIII single-molecule magnets (SMMs). This structural transformation involves lattice solvents which leads to significant changes in the color and magnetic properties. Additionally, the relaxation dynamics of mononuclear DyIII compounds are perceptibly fine-tuned by the modification of ß-diketonate ligands. The uniaxial magnetic anisotropies, magneto-structural correlations and the relaxation mechanism were investigated by magnetic studies and ab initio calculations. These experimental and theoretical studies indicate that compound 2 exhibits the best magnetic properties in compounds 1-4. The experimental observation is supported by the theoretical prediction of QTM time (τZeeQTM) as theτZeeQTM of 2 is remarkably longer than those of the other three compounds by an order of magnitude. This means that, compared with 1, 3, and 4, the magnetic relaxation of 2 is significantly slower. Meanwhile, 2 has the largest value of axial ESP (the axial electrostatic potential), which supports the smallest gXY value in these compounds, resulting in better SMM properties. The present results offer a systematic synthesis regulation to change the magnetization dynamics and further understand magneto-structural correlations for DyIII SMMs.

High temperature quantum tunnelling of magnetization and thousand kelvin anisotropy barrier in a Dy2 single-molecule magnet.

We report here a dinuclear DyIII iodine-bridged single-molecule magnet self-assembled by cis/trans coordination chemistry that displays a large anisotropy barrier of ca. 1300 K and a hysteresis opening temperature of 16 K. High temperature quantum tunnelling of magnetization is observed up to 56 K in zero-field and explained by the combination of the large anisotropy barrier and the local transverse field at the trans site. The results provide a model for thorough understanding of the effect of electronic structure on the magnetic behavior of lanthanide complexes.

Improved Detonation Performance Via Coordination Substitution: Synthesis and Characterization of Two New Green Energetic Coordination Polymers.

In this work, a new energetic coordination polymer (ECP), [Cu(HBTI)(H2O)]n (1) (H3BTI = 4,5-bistetrazole-imidazole), was synthesized by a hydrothermal method. Due to the existence of coordination water molecules in 1, however, its energy density was limited, which led to the insufficient detonation performance. To further improve its detonation performance, [Cu(H2BTI)(NO3)]n (2) was then obtained by substituting the coordinated water molecule in 1 with nitrate through the coordination substitution reaction under acidic conditions. The structures of two ECPs were respectively characterized using X-ray single-crystal diffraction, and the theoretical density of 2 (2.227 g·cm-3) was greater than 1 (1.851 g·cm-3). Thermogravimetric analyses showed that 2 has a one-step rapid weight loss process compared with the two-step slow weight loss process of 1. The theoretical calculations indicated that the detonation performances of 2 were better than those of 1. Moreover, the promotion effects of two ECPs on the combustion decomposition of ammonium perchlorate were studied using a differential scanning calorimetry method.

Suppressed Jahn-Teller Distortion in MnCo2 O4 @Ni2 P Heterostructures to Promote the Overall Water Splitting.

Jahn-Teller distortion in cobalt based spinel electrocatalysts causes poor activity and stability in potentially promising catalysts for water splitting. Here, a novel strategy to resolve this problem by interface engineering is reported, in which, Jahn-Teller distortion in MnCo2 O4 is significantly suppressed by in situ growth Ni2 P nanosheets onto the MnCo2 O4 . The significance of interface engineering in suppressing Jahn-Teller distortion of Mn3+ is further investigated by X-ray photoelectron spectroscopy, the resulting increased catalytic activity and the effects of suppressed distortion demonstrated by density functional theory calculations. The resulting MnCo2 O4 @Ni2 P heterostructures exhibit superior electrocatalytic activity for the both oxygen evolution reaction and hydrogen evolution reaction with small overpotentials of 240 and 57 mV at 10 mA cm-2 , respectively. Furthermore, the heterogeneous composite electrode demonstrates a superior current density of 10 mA cm-2 at a voltage of 1.63 V with excellent durability in a water splitting cell.

Synergistic effect of mixed ligands on the anisotropy axis of two dinuclear dysprosium complexes.

We present the syntheses, crystal structures, magnetic properties and theoretical calculations performed on two dinuclear dysprosium complexes with formulas Dy2(L1)2(L2)2(CH3CH2OH)(CH3OH) (1) and Dy2(L1)2(L3)2(CH3OH)2·1.5CH3OH (2). Single-crystal X-ray structural data analyses showed that both complexes contain two nonequivalent dysprosium ions bridged by two phenolate oxygen atoms. In both complexes, each dysprosium site adopts a N2O6 coordination constitution and triangular dodecahedron (D2d) configuration geometry with different distortion degree. Both complexes display single-molecule magnet behavior manifested by frequency-dependent out-of-phase alternating current susceptibility signal peaks under a zero-applied dc field. The effective energy barrier of the magnetization reversal and relaxation time values are 61 K, 7.1 × 10-6 s (1) and 51 K, 1.9 × 10-6 s (2), respectively. Theoretical calculations revealed a drastic discrepancy between the orientations of the anisotropy axis of the Dy2 ion observed in these two dinuclear complexes, resulting from the different spatial arrangements of the mixed ligands in the core structure.

An Inconspicuous Six-Coordinate Neutral DyIII Single-Ion Magnet with Remarkable Magnetic Anisotropy and Stability.

It is a crucial challenge to address both magnetic anisotropy and stability for single-molecule magnets (SMMs) used in next-generation nanodevices. Highly axial lanthanide SMMs with neutral charge and moderate coordination numbers represent promising magnetic materials. Here, using iodide ions with large volume and low surface charge density as weak donors, we report a six-coordinate neutral dysprosium SMM [Dy(Cy3PO)2I3(CH3CN)] with a certain degree of stability exhibiting a huge thermal barrier of 1062 K and hysteresis loops open up to 9 K. Through the elaborate reduction of ligand field strength, an apparent strongly axial crystal field is provided which elicits prominent crystal-field splitting and high axiality with the thermally activated relaxation via the third-excited Kramers' doublet. Moreover, the profound influence of strong equatorial ligand substitution on the electronic structure and relaxation pathway is clearly explored in DyIII analogues. The result suggests the great potential of the reducing the transverse ligand field in the improvement of SMMs performance.