γ-MnO2 as an Electron Reservoir for RuO2 Oxygen Evolution Catalyst in Acidic Media.

Developing highly active and durable catalysts in acid conditions remains an urgent issue due to the sluggish kinetics of oxygen evolution reaction (OER). Although RuO2 has been a state-of-the-art commercial catalyst for OER, it encounters poor stability and high cost. In this study, the electronic reservoir regulation strategy is proposed to promote the performance of acidic water oxidation via constructing a RuO2/MnO2 heterostructure supported on carbon cloth (CC) (abbreviated as RuO2/MnO2/CC). Theoretical and experimental results reveal that MnO2 acts as an electron reservoir for RuO2. It facilitates electron transfer from RuO2, enhancing its activity prior to OER, and donates electrons to RuO2, improving its stability after OER. Consequently, RuO2/MnO2/CC exhibits better performance compared to commercial RuO2, with an ultrasmall overpotential of 189 mV at 10 mA cm-2 and no signs of deactivation even after 800 h of electrolysis in 0.5 m H2SO4 at 10 mA cm-2. When applied as the anode in a proton exchange membrane water electrolyzer, the cost-efficient RuO2/MnO2/CC catalyst only requires a cell voltage of 1.661 V to achieve the water-splitting current of 1 A cm-2, and the noble metal cost is as low as US$ 0.00962 cm-2, indicating potential for practical applications.

A Universal Synthesis Strategy for Lanthanide Sulfide Nanocrystals with Efficient Photocatalytic Hydrogen Production.

As an important lanthanide (Ln)-based functional materials, the Ln chalcogenides possess unique properties and various applications. However, the controllable synthesis of Ln chalcogenide nanocrystals still faces great challenges because of the rather poor affinity between Ln and chalcogenide ions (S, Se, Te) as well as strong preference of combination with existed oxygen. Herein, a facile but general heterogeneous nucleation synthetic strategy is established toward a series of colloidal ternary Cu Ln sulfides nanocrystals using the Ln dithiocarbamates and CuI as precursors. To extend this synthetic protocol, similar strategy is used to prepare six kinds of high quality CuLnS2 nanocrystals, while the bulk ones are only obtained by the traditional solid-state reaction at rigorous condition. Importantly, high-entropy nanocrystals CuLnS2 and CuEux Ln2-x S3 which contain six Ln elements (Nd, Sm, Gd, Tb, Dy) are readily obtained by the co-decomposed process attributed to their similar diffusion speed. As a proof-of-concept application, CuEu2 S3 nanocrystals showed efficient photocatalytic hydrogen production properties.

Pyrazine-Functionalized Donor-Acceptor Covalent Organic Frameworks for Enhanced Photocatalytic H2 Evolution with High Proton Transport.

The well-defined 2D or 3D structure of covalent organic frameworks (COFs) makes it have great potential in photoelectric conversion and ions conduction fields. Herein, a new donor-accepter (D-A) COF material, named PyPz-COF, constructed from electron donor 4,4',4″,4'″-(pyrene-1,3,6,8-tetrayl)tetraaniline and electron accepter 4,4'-(pyrazine-2,5-diyl)dibenzaldehyde with an ordered and stable π-conjugated structure is reported. Interestingly, the introduction of pyrazine ring endows the PyPz-COF a distinct optical, electrochemical, charge-transfer properties, and also brings plentiful CN groups that enrich the proton by hydrogen bonds to enhance the photocatalysis performance. Thus, PyPz-COF exhibits a significantly improved photocatalytic hydrogen generation performance up to 7542 µmol g-1 h-1 with Pt as cocatalyst, also in clear contrast to that of PyTp-COF without pyrazine introduction (1714 µmol g-1 h-1 ). Moreover, the abundant nitrogen sites of the pyrazine ring and the well-defined 1D nanochannels enable the as-prepared COFs to immobilize H3 PO4 proton carriers in COFs through hydrogen bond confinement. The resulting material has an impressive proton conduction up to 8.10 × 10-2 S cm-1 at 353 K, 98% RH. This work will inspire the design and synthesis of COF-based materials with both efficient photocatalysis and proton conduction performance in the future.

Inorganic-Organic Hybrid Multifunctional Solid Electrolyte Interphase Layers for Dendrite-Free Sodium Metal Anodes.

Constructing a stable and robust solid electrolyte interphase (SEI) is crucial for achieving dendrite-free sodium metal anodes and high-performance sodium batteries. However, maintaining the integrity of SEI during prolonged cycle life under high current densities poses a significant challenge. In this study, we propose an integrated multifunctional SEI layer with inorganic/organic hybrid construction (IOHL-Na) to enhance the durability of sodium metal anode during reduplicative plating/stripping processes. The inorganic components with high mechanical strength and strong sodiophilicity demonstrate optimized ionic conduction efficiency and dendrite inhibition ability. Simultaneously, the organic component contributes to the formation of a dense and elastic membrane structure, preventing fracture and delamination issues during volume fluctuations. The symmetrical batteries of IOHL-Na achieve stable cycling over 2000 hours with an extremely low voltage hysteresis of around 15.8 mV at a high current density of 4 mA cm-2 . Moreover, the Na-O2 batteries sustain exceptional long-term stability and impressive capacity retention, exploiting a promising approach for constructing durable SEI and dendrite-free sodium metal anodes.

Designable Guest-Molecule Encapsulation in Metal-Organic Frameworks for Proton Conductivity.

Metal-organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs' proton conductivity are also listed.

Bifunctional Metal-Organic Framework Functionalized by Dimethylamine Cations: Proton Conduction and Iodine Vapor Adsorption.

A metal-organic framework, {Zn3(BTB)2(µ3-OH)[(CH3)2NH2](H2O)}n (1), was synthesized based on H3BTB (1,3,5-tri(4-carboxyphenyl)benzene). An AC impedance test proves that 1 has a relatively high conductivity performance of 1.52 × 10-3 S·cm-1 at 338 K and 98% RH. The proton conductivity of the composite film 1@CS-9 (CS = chitosan) reaches 1.84 × 10-1 S·cm-1 at 328 K and 98% RH. In addition, 1 is discovered to have a good adsorption effect on iodine vapor, and the adsorption capacity reaches 726 mg·g-1. The multifunctionality caused by dimethylamine cations was investigated for the first time, which has implications for multifunctionality generated by host-guest molecules.

Enantiomorphic Single Crystals of Linear Lead(II) Bromide Perovskitoids with White Circularly Polarized Emission.

Chiroptical hybrid organic-inorganic perovskites are emerging as a new class of promising materials with mirror optical signal responses for optoelectronic applications. However, chiroptical white-emission materials have been scarcely unearthed. Herein, four pairs of hybrid lead(II) bromide perovskitoids were obtained, namely, (R)- and (S)-(H2 MPz)PbBr4 (R/S-MPz=(R)-(-)/(S)-(+)-2-methylpiperazine) (1 and 2), (R)- and (S)-(H2 MPz)3 Pb2 Br10 ⋅2 DMAc (3 and 4), (R)- and (S)-(H2 MPz)PbBr4 ⋅0.5 MeCN (5 and 6) and (R)- and (S)-(H2 MPz)2 Pb2 Br8 ⋅DCM (7 and 8). Notably, they all exhibit ultrabroadband emission and chiroptical signals. Perovskitoids 3-6 even achieve white circularly polarized emission with a high dissymmetric factor (glum ) (±3×10-3 for 3 and 4; ±8×10-3 for 5 and 6). This new type of hybrid perovskitoids will attract attention and find applications in chiroptical fields because of the extensively and easily tunable photophysical properties.

Promotion of Proton Conductivity by Encapsulation of Metal-Organic Polyhedra in Metal-Organic Frameworks.

A Zr-based metal-organic polyhedron (MOP) was self-assembled in a porous MOF host, DUT-68, successfully to synthesize MOP-1@DUT-68. The MOP guest (MOP-1) has a diameter of about 20 Å, larger than that of the square windows (pore sizes of ∼14 Å) of DUT-68 but smaller than that of the rhombicuboctahedral cage (27.7 Å), which means that the migration and leaching of MOP-1 could be effectively prohibited if MOP-1 is encapsulated in the MOF's cavities. The proton conductivity of MOP-1@DUT-68 is 1.14×10-3  S cm-1 (at 80 °C under 98 % relative humidity), which is three orders of magnitude higher than that of DUT-68. Compared with MOP-1⊂DUT-68, which was synthesized by impregnation, MOP-1@DUT-68 is more prone to form faster proton-conduction pathways and thus provides higher proton conductivity.

High Proton Conductivity of a Cadmium Metal-Organic Framework Constructed from Pyrazolecarboxylate and Its Hybrid Membrane.

A new type of metal-organic framework, [Cd2(pdc)(H2O)(DMA)2]n (pdc = 3,5-pyrazoledicarboxylic acid; DMA = dimethylamine), named Cd-MOF, was synthesized and characterized. There are regular rectangular pore channels containing a large number of dimethylamine cations in the crystal structure. AC impedance test results show the proton conductivity of Cd-MOF reaches 1.15 × 10-3 S cm-1 at 363 K and 98% RH. In order for its application in fuel cells, the Cd-MOF was introduced into a sulfonated polyphenylene oxide matrix to prepare a hybrid membrane, and the proton conductivity of the hybrid membrane has a high value of 2.64 × 10-1 S cm-1 at 343 K and 98% RH, which is higher than those of most MOF polymer hybrid membranes. The proton conductivity of the hybrid membrane of the SPPO polymer still maintains a certain degree of stability in a wide temperature range. To the best of our knowledge, it is the first proton exchange membrane that combines pyrazolecarboxylate cadmium MOFs and an SPPO polymer with high proton conductivity and good stability. This research may help to further develop the application of MOFs in the field of proton exchange membrane fuel cells.

2D europium coordination polymer as a regenerable fluorescence probe for efficiently detecting fipronil.

Recently, considerable attention has been paid to European eggs that were found to contain the poisonous insecticide fipronil. Excessive consumption of fipronil can harm the human body, in particular, the liver, thyroid, nervous system and kidneys. As a consequence, there is an urgent need to develop a method to detect fipronil. In this work, a lanthanide coordination polymer [Eu(SIP)(H2O)4]n (1) (NaH2SIP = 5-sulfoisophthalic acid monosodium salt) was synthesized and characterized by single-crystal X-ray crystallography, elemental analysis, infrared spectrum and powder X-ray diffractions. The X-ray studies show that 1 is a two-dimensional layered structure, which is constructed of fused {[Eu(H2O)4]3(SIP)3} pseudo-hexagonal grids. The luminescence properties of 1 exhibit effective recognition for fipronil in methanol solution. Furthermore, a wide linear range (10-6-10-4 M), a low detection limit of 0.8 µM, high selectivity and excellent recyclability, reveal that 1 can potentially act as a luminescence-based sensor for quantitative and highly sensitive detection of fipronil. To the best of our knowledge, it is the first time that a metal-organic coordination polymer, as a fluorescent-based probe, has been used for the detection of fipronil. Moreover, fluorescent-based test papers of 1 have also been prepared, which can be regarded as a simple and practical method for detecting fipronil.

Alkylamine-Templated Niccolite Frameworks of [GaIIIMII(HCOO)6]- (M = Fe, Ni): Structure, Magnetism, and Dielectricity.

The five heterometallic formate frameworks [EtA][GaIIIFeII(HCOO)6] (1; EtA = CH3CH2NH3+), [DMA][GaIIIFeII(HCOO)6] (2; DMA = (CH3)2NH2+), [DEtA][GaIIIFeII(HCOO)6] (3; DEtA = (CH3CH2)2NH2+), [MA][GaIIINiII(HCOO)6] (4; MA = CH3NH3+), and [DMA][GaIIINiII(HCOO)6] (5) were synthesized through solvothermal methods. Complexes 1-5 are isotructural, and all crystallize in the trigonal P3̅1 c space group. Each metal center is 6-connected, with each HCOO- bridging ligand in an anti-anti mode to build a three-dimensional niccolite-like architecture. All of the complexes exhibit weak ferromagnetism at low temperature. A variable-temperature (VT) dielectric study indicates that the dielectric anomaly is induced by the freezing of motions from the protonated amines during the freezing process.

Ferroelastic Phase Transition and Switchable Dielectric Constant in Heterometallic Niccolite Formate Frameworks.

Four heterometallic formate frameworks templated by various alkylamine cations with the general formula [cat][GaIIIMnII(HCOO)6] {cat is MA (CH3NH3+) for 1, DMA [(CH3)2NH2+] for 2, EtA (CH3CH2NH3+) for 3, and DEtA [(CH3CH2)2NH2+] for 4} have been prepared and characterized by X-ray diffraction, differential scanning calorimetry, and dielectric studies. All of the complexes have niccolite-like structures, which possess the same [GaMn(HCOO)6]- anionic framework with binodal (412·63)(49·66) topology; only the counterions in the cavity are different. Complex 4 undergoes a reversible ferroelastic phase transition around 220 K accompanied by a thermally switchable dielectric constant transition triggered by the freezing of the order-disorder DEtA cations.

Composite Quasi-Solid-State Electrolytes with Organic-Inorganic Interface Engineering for Fast Ion Transport in Dendrite-Free Sodium Metal Batteries.

Quasi-solid-state electrolytes (QSSE) are a promising candidate for addressing the limitations of liquid and solid electrolytes. However, different ion transport capacities between liquid solvents and polymers can cause localized heterogeneous distribution of Na+ fluxes. In addition, the continuous side reactions occurring at the interface between QSSE and sodium anode lead to uncontrollable dendrites growth. Herein, a novel strategy is designed to integrate the composite electrospun membrane of Na3Zr2Si2PO12 and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) into QSSE, aiming to introduce new fast ion conducting channels at the organic-inorganic interface. The efficient ion transfer pathways can effectively promote the homogenization of ion migration, enabling composite QSSE to achieve an ultrahigh ionic conductivity of 4.1 mS cm-1 at room temperature, with a Na+ transference number as high as 0.54. Moreover, the PVDF-HFP is preferentially reduced upon contact with the sodium anode to form a "NaF-rich" solid electrolyte interphase, which effectively suppresses the growth of dendrites. The synergistic combination of multiple strategies can realize exceptional long-term cycling stability in both sodium symmetric batteries (≈700 h) and full batteries (2100 cycles). This study provides a new insight for constructing high performance and dendrite-free solid-state sodium metal batteries.

Anchoring of Fe-MIL-101-NH2 to the Polymer Membrane Matrix through the Hinsberg Reaction to Promote Conductivity of SPEEK Membranes.

SCPEEK@MOF proton exchange membranes, where SCPEEK is sulfinyl chloride polyether ether ketone and MOF is a metal-organic framework, were prepared by doping Fe-MIL-101-NH2 into polymers. The amino group in the MOF and the -SOCl2 group in thionyl chloride polyether ether ketone cross-link to form a covalent bond through the Hinsberg reaction, and the prepared composite membrane has stronger stability than other electrostatic interactions and simple physical doping composite membranes. The formation of covalent bonds improves the water absorption of the composite membrane, which makes it easy for water molecules to form hydrogen bonds. Moreover, SPEEK as a proton conductive polymer and the synergy of MOFs improve the proton conductivity of composite membranes. The composite membranes were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The swelling rate, water absorption, mechanical stability, ion exchange capacity, and proton conductivity of the pure sulfonated polyether ether ketone (SPEEK) membrane were compared with those of the mechanically doped SPEEK/MOF membrane and the composite membrane SCPEEK@MOF doped with different ratios of Fe-MIL-101-NH2, and all of the SCPEEK@MOF showed superior performance. When the Fe-MIL-101-NH2 loading rate of the composite membrane is 2%, the proton conductivity of the composite membrane can reach 0.202 S cm-1 at 363 K and a 98% relative humidity, which is much higher than that of the SPEEK/MOF membrane obtained by simple physical doping under the same conditions.

Synthesis and proton-conductive behaviour of two MOFs with covalently bonded imidazoles in the channels.

Immobilization of imidazole molecules as proton carriers into MOFs to facilitate proton conduction is a general strategy for developing high proton conductive materials. Herein, we designed two imidazole substituted phthalic acid ligands and constructed two novel MOFs, {[Zr6(OH)16(H3L1)4]Cl8·20H2O}n [Zr-MOF; H3L1 = 2-(1H-imidazol-4-yl) methylaminoterephthalic acid] and {Gd(HCOO)(H2L2)2}n [Gd-MOF; H3L2 = 5-(1H-imidazol-4-yl)methylaminoisophthalic acid] and fully studied their porous nature, stability and water-assisted proton conduction. The resulting Zr-MOF exhibits a high proton conductivity of 1.82 × 10-2 S cm-1 at 98% RH and 80 °C, while Gd-MOF has a proton conductivity of 3.01 × 10-3 S cm-1 at 98% RH and 60 °C.

Syntheses, structures, and magnetic and luminescence properties of a new Dy(III)-based single-ion magnet.

Three new Ln(III) complexes based on 2,2'-bipyridine [Ln(hfac)3(bpy)] (Ln = Dy (1), Tb (2), or Ho (3); hfac = hexafluoroacetylacetonate; and bpy = 2,2'-bipyridine) have been synthesized and characterized structurally and magnetically. Single-crystal X-ray analysis shows that all these complexes contain one [Ln(hfac)3(bpy)] unit in which a center Ln(III) ion is surrounded with a slightly distorted square-antiprismatic LnO6N2 coordination sphere formed by three bischelate hfac anions and one bpy ligand. Both static and dynamic magnetic properties were studied for complex 1, which is proved to be a new single-ion magnet. The luminescence characterizations of complexes 1 and 2 are also studied in this paper.

High Proton Conductivity of the UiO-66-NH2-SPES Composite Membrane Prepared by Covalent Cross-Linking.

A sulfonated poly(ethersulfone) (SPES)-metal-organic framework (MOF) film with excellent proton conductivity was synthesized by anchoring UiO-66-NH2 to the main chain of the aromatic polymer through the Hinsberg reaction. The chemical bond was formed between the amino group in MOFs and the -SO2Cl group in chlorosulfonated poly(ethersulfones) to conduct protons in the proton channel of the membrane, making the membrane have excellent proton conductivity. UiO-66-NH2 is successfully prepared as a result of the consistency of the experimental and simulated powder X-ray diffraction (PXRD) patterns of MOFs. The existence of absorption peaks of characteristic functional groups in Fourier transform infrared (FTIR) spectra proved the successful preparation of SPES, PES-SO2Cl, and a composite film. The results of the AC impedance test indicate that the composite film with a 3% mass fraction has the best proton conductivity of 0.215 S·cm-1, which is 6.2 times higher than that of the blended film without a chemical bond at 98% RH and 353 K. To our knowledge, there are rarely any reports on the preparation of a composite membrane by directly linking MOFs and the membrane matrix with chemical bonds. This work provides a good way to synthesize the highly conductive proton exchange film.

A dual-function Cd-MOF with high proton conduction and excellent fluorescence detection of pyridine.

Metal-organic frameworks have great potential in the field of proton conducting materials and fluorescent probes due to their structural tunability and designability. A novel water-stable metal organic framework material [Cd2(Hdpb)(H2O)3] (Cd-MOF) was synthesized based on H5dpb (H5dpb = 3,5-diphosphonobenzoic acid) and Cd2+ ions. Cd2+ ions are connected with phosphonates and carboxyl groups of H5dpb to form an infinitely extended 1D chain, which is further connected by the Hdpb4- ligand and coordinated water to form a three-dimensional network structure. There are hydrogen bond networks in the 3D structure of the Cd-MOF, which are favorable for proton transfer, achieving its maximum proton conductivity of 2.97 × 10-3 S cm-1 at 338 K and 98% relative humidity (RH). To realize its application in fuel cells, the Cd-MOF was introduced into the chitosan (CS) matrix, and a series of composite membranes (Cd-MOF@CS-X) with high proton conductivity were obtained. The results of AC impedance show that the proton conductivity of Cd-MOF@CS-5 reaches 3.55 × 10-1 S cm-1 at 358 K and 98% RH, which is comparable to the highest values reported for MOF-polymer complexes. Moreover, the Cd-MOF can be used as a selective fluorescent probe for pyridine detection, and its detection limit can reach 1.0 × 10-6 M. A bifunctional MOF with proton conduction and pyridine recognition is reported for the first time, and has important reference value for the practical application of functional MOFs in both electrochemical and luminescence sensing.

Slow magnetic relaxation in a Dy3 triangle and a bistriangular Dy6 cluster.

Two lanthanide single-molecule magnets (SMMs) [Dy3(µ3-OH)(HL-1)3(H2O)3](NO3)2·3H3O (1, H3L-1 = (E)-3-(((8-hydroxyquinolin-2-yl)methylene)amino)propane-1,2-diol) and [Dy6(µ3-OH)4(H2L-2)4(HL-2)2(L-2)2] (2, H3L-2 = (E)-2-hydroxy-N'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide) were synthesized and characterized structurally and magnetically. Complex 1 contains a triangular Dy3 core in which the three Dy3+ ions share a µ3-OH- anion and the deprotonated ligands of (HL-1)2- serve both capping and bridging functions, while 2 displays a centrosymmetric hexanuclear DyIII structure with two similar Dy3 triangular cores ligated by two fully deprotonated (L-2)3- ligands, each of which shares two µ3-OH- anions. All the DyIII ions are eight-coordinated with quasi D2d or C2v symmetry. Magnetic studies reveal that 1 exhibited two-step magnetic relaxation under an applied dc field of 800 Oe, with effective energy barriers of 40.1 and 31.0 K for the slow relaxation (SR) and fast relaxation regimes (FR), respectively. Meanwhile, 2 only showed a tail of slow magnetic relaxation at above 2 K. Ab initio calculations have been carried out to show the nature of their different magnetic properties.

Two novel cyanide-bridged bimetallic magnetic chains derived from manganese(III) Schiff bases and hexacyanochromate(III) building blocks.

Two novel complexes, [{Mn(salen)}(2){Mn(salen)(CH(3)OH)}{Cr(CN)(6)}](n)·2nCH(3)CN·nCH(3)OH (1) and [Mn(5-Clsalmen)(CH(3)OH)(H(2)O)](2n)[{Mn(5-Clsalmen)(µ-CN)}Cr(CN)(5)](n)·5.5nH(2)O (2) (salen(2-) = N,N'-ethylene-bis(salicylideneiminato) dianion; 5-Clsalmen(2-) = N,N'-(1-methylethylene)-bis(5-chlorosalicylideneiminato) dianion), were synthesized and structurally characterized by X-ray single-crystal diffraction. The structural analyses show that complex 1 consists of one-dimensional (1D) alternating chains formed by the [{Cr(CN)(6)}{Mn(salen)}(4){Mn(salen)(CH(3)OH)}(2)](3+) heptanuclear cations and [Cr(CN)(6)](3-) anions. While in complex 2, the hexacyanochromate(III) anion acts as a bis-monodentate ligand through two trans-cyano groups to bridge two [Mn(5-Clsalmen)](+) cations to form a straight chain. The magnetic analysis indicates that complex 1 shows three-dimensional (3D) antiferromagnetic ordering with the Néel temperature of 5.0 K, and it is a metamagnet displaying antiferromagnetic to ferromagnetic transition at a critical field of about 2.6 kOe at 2 K. Complex 2 behaves as a molecular magnet with Tc = 3.0 K.