Four POM-Viologen Color-Changing Materials with Fast Color Response under Various External Stimuli.

Four kinds of polyoxometalate (POM)-viologen compounds were synthesized by hydrothermal method, namely (1-cby)2·[H2(SiMo12O40)]·2H2O (1), (1-cby)2·[H2(SiW12O40)]·2H2O (2), (1-cby)2·(1,1'-bcby)2·{H4[Co4(H2O)2(PW9O34)2]}·12H2O (3), (1-cby)·(1,1'-bcby)·[H(α-PW11O39)CoII(1-cby)]·8H2O (4) (1-cby·Br = 1-Cyclopropylmethyl-[4,4']bipyridinyl-1-ium bromide, 1,1'-bcby·Br = 1,1'-Bis-cyclopropylmethyl-[4,4']bipyridinyl-1-ium bromide). These four POM-viologen compounds exhibit one-dimensional supramolecular network structures. Especially, compound 3 contains a rare sandwich POM subunit {Co4(H2O)2(PW9O34)2}10-. These four compounds can be used as color-changing materials, and they all exhibit noticeable color changes upon exposure to light, heat, and electricity. The discoloration mechanism involves viologen derivatives with electron-deficient properties accepting electrons from POM with electron-rich properties under external stimulation, leading to the formation of viologen free radicals. Among them, compounds 1 and 2 also have good properties for ink-free erasable printing, double anticounterfeiting, and ultraviolet detector because of their rapid color response to ultraviolet (UV) light. In addition, compounds 1-4 also show different color changes in the detection of volatile amines.

Four polyoxomolybdated-based 3D compounds as supercapacitors and amperometric sensors.

Four polyoxomolybdated compounds based on Tetp (Tetp = 4-[4-(2-Thiophen-2-yl-ethyl)-4H-[1, 2, 4]triazole-3-yl]-pyridine), namely [Zn(Tetp)2(H2O)2][(ß-Mo8O26)0.5] (Zn-Mo8), [Co(Tetp)2(H2O)2][(ß-Mo8O26)0.5] (Co-Mo8), [Cu4(Tetp)6(H2O)2]{H3[K(H2O)3](θ-Mo8O26)(Mo12O40)}·8H2O (Cu-Mo20) and [Cu3(Tetp)3][PMo12O40]·H2O (Cu-PMo12) are synthesized by hydrothermal methods and are used as electrode materials for supercapacitors(SCs) and electrochemical sensors. Inserting polyoxometalates (POMs) with redox active sites into transition metal compounds (TMCs) can improve the internal ion/electron transfer rate, thus effectively enhancing the electrochemical performance. Compared with the parent POMs, four compounds exhibit excellent electrochemical properties. In particular, Cu-PMo12 shows an excellent specific capacitance (812.3 F g-1 at 1 A g-1) and stability (94.42%), as well as a wide detection range (0.05 to 1250 µM) and a low detection limit (0.057 µM) for NO2- sensing.

Photo-, Thermo-, Electrochromic, Erasable Inkless Printing, Ions Detection, and UV Detector Properties of Viologen Compounds Based on Homomolybdate/Keggin POMs.

Three POMs-based viologen compounds with different structures were successfully constructed under solvothermal and hydrothermal conditions, [Cu(1,4-cby)2(H2O)0.5(ß-Mo8O26)0.5]·C3H7NO·3H2O (1), [H2(1,4-cby)2]·(ß-Mo8O26) (2) (1,4-cby·Cl = 1-(4-carboxybenzyl)-4,4'-bipyridine chloride), [H2(1,4-cbyy)2]·(SiMo12O40) (3) (1,4-cbyy·Cl = 1-(4-cyanobenzyl)-4,4'-bipyridine chloride). Compound 1 is a structure with the number "eight-like" metal-organic chain with Cu as the nodes, and compounds 2 and 3 are fascinating structures connected by hydrogen bonding interactions. More importantly, compounds 1-3 exhibit a good response to both light and electricity and the thermal response of compound 1 was also studied. The reasons for the response of compounds 1-3 to external stimuli were analyzed through methods such as UV-Vis, EPR, and XPS. In addition, the transient photocurrent response results of compounds 1-3 are the same as those obtained from kinetic calculations. Meanwhile, the coated filter paper based on compound 3 has been successfully applied in erasable inkless printing and anti-counterfeiting, the test paper of 3 can also detect metal ions, and the films based on compounds 1-3 are a flexible and portable ultraviolet (UV) detector.

Electrocatalytic and Hg2+ Fluorescence Identifiable Bifunctional Sensors for a Series of Keggin Compounds.

By using a 2,2'-dimethyl-4,4'-bithiazole (dm4bt) ligand, Keggin polyanions, and different metal ions, nine Keggin-based compounds, namely, {[Ag(dm4bt)2][Ag2(dm4bt)3]}2(PW12O40)(H2PWV2WVI10O40) (1), [CuI(dm4bt)2][CuII(dm4bt)2(PW12O40)] (2), [CuI(dm4bt)2]4(SiW12O40) (3), {[Zn(dm4bt)2]2(SiW12O40)} (4), [Zn(dm4bt)2(H2O)]2(HPMoV2MoVI10O40)·2H2O (5), [Zn(dm4bt)2(Mo2O7)] (6), [Cd(dm4bt)3][Cd(dm4bt)2(H2O)(PMo12O40)]2·2H2O (7), [Cd(dm4bt)3](PMo12O40)·(Hdm4bt) (8), and [Cd(dm4bt)2(H2O)2]2(HPMoV2MoVI10O40)·2H2O (9), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectroscopy, and elemental analyses. Compounds 1-9 are zero-dimensional structures except compound 6, which exhibits a one-dimensional structure. In compound 1, there are three isolated subunits: Keggin anions, binuclear [Ag2(dm4bt)3]2+, and mononuclear [Ag(dm4bt)2]+ clusters. The binuclear [Ag2(dm4bt)3]2+ cluster has a Ag-Ag bond. In compound 2, a monosupporting anion {[CuII(dm4bt)2](PW12O40)}- and an isolated [Cu(dm4bt)2]+ cluster exist. By changing the transition metal ions, we obtained two different structures: a supramolecular 3 and a bisupporting anion in 4. By a one-pot method, we successfully obtained compounds 5 and 6, 7 and 8, respectively. In compound 5, the [Zn(dm4bt)2(H2O)]2+ subunit links adjacent PMo12 anions via S···O interactions to form a one-dimensional (1D) supramolecular chain. In compound 6, some PMo12 ions have transformed to [Mo2O7] n2 n- chains. The [Zn(dm4bt)2]2+ clusters buckle up and down the chain. Compound 7 has a monosupporting anion and an isolated [Cd(dm4bt)3]2+ cluster. Compound 8 has isolated anions and [Cd(dm4bt)3]2+ clusters. By changing the pH of 7 and 8, a distinct supramolecular compound 9 was obtained. Additionally, the optical band gap, electrochemical, and photocatalytic properties of 1-9 have been investigated in detail. The carbon paste electrodes can be used as bifunctional amperometric and fluorescence sensors for recognition of Hg2+. The n-CPEs as electrochemical sensors can show accurate selectivity for NO2- ions in some common ions. In the fluorescence sensor experiment, fluorescence intensities decrease more than 80% when quenched by Hg2+.

A series of viologen/POM materials with discoloration properties under the stimulation of X-ray, UV, electricity, and organic amines.

At present, viologen-based compounds can undergo reversible chemical/physical changes under external stimuli such as light and electricity. This makes these compounds have potential applications in smart windows, displays, and sensors. In order to obtain such materials, three viologen-POM inorganic-organic hybrid compounds have been successfully synthesized by a hydrothermal method, namely {[Cu2(cybpy)8(α-P2W18O62)2}·18H2O (1), (Hbpy)·(cybpy)·[H4(α-P2W18O62)]}·32H2O (2) and {(Hcybpy)2(ß-Mo8O26)}·2H2O (3) (cybpy·Br = 1-cyclobutylmethyl-[4,4']bipyridinyl-1-ium bromide, bpy = 4,4'-bipyridine). Three compounds exhibit good discoloration behaviors under various external stimuli, especially under the stimulation of X-ray, UV, electricity, and organic amines. In addition, in order to promote the compounds in the actual production of more applications, they were doped into the polymer matrix to construct hybrid films, which not only have the same response to external stimulation but also increase the repeatability of the photochromic process. Moreover, 1-3 powder samples in ethanol solution were ultrasonic treated and deposited on filter paper, which can be successfully used in erasable inkless printing.

The applications of Keggin-based metal-organic compounds in sensing and catalysis.

Environmental pollution and energy problems caused by excessive use of fossil fuels deviate from the theme of green and sustainable development. It is very promising to detect small molecules or catalyze the conversion of pollutants to obtain renewable energy by using photoelectric technology. Therefore, there is an urgent requirement to develop materials with low detection limits and high catalytic performance. Keggin polyoxometalate-based metal-organic compounds (POMOCs) hold great promise for sensing, and catalytic applications due to their controllable structure, remarkable reversible multi-electron transfer capability and multi-component synergistic activity. In this review, the applications of Keggin POMOCs in photocatalytic/electrocatalytic conversion of energy materials and the detection of metal ion/inorganic molecule are introduced. The different mechanisms of Keggin POM units and MOF units in sensors and catalysis are discussed. Additionally, the prospects of the Keggin POMOCs as electrode materials or catalysts for enhancing the performance of sensors and catalysts are discussed, which will provide a platform for further development of advanced Keggin POMOC material-based sensors and catalytic systems.

Four octamolybdate compounds with properties of organic dye adsorption and photocatalytic reduction of Cr(VI).

Hydrothermal synthesis was used to create four different POM-based compounds, namely {[Co(Hptpm)2(ß-Mo8O26)0.5(ξ-Mo8O26)0.5]}·H2O (1), [Co(Hptpm)2(δ-Mo8O26)]·H2O (2), [Co(Hptpm)2(ß-Mo8O26)] (3) and [Zn(Hptpm)2(ß-Mo8O26)] (4) (ptpm = 4-[3-(3-pyridine-2-yl-[1,2,4]triazol-4-yl)-propyl]-morpholine). 1-4 containing different octamolybdate isomers were characterized. Compounds 1-4 showed good electrochemical performance and can be utilized as bifunctional sensors for NO2-, H2O2, Cr(VI) and Fe(III). Taking compound 1 as an example, the detection limits are 0.081 µM for NO2-, 0.072 µM for H2O2, 0.054 µM for Cr(VI) and 0.063 µM for Fe(III), respectively. Compounds 1-4 have good capacitance. Moreover, compounds 1-4 also show good adsorption properties for organic cationic dyes. The cationic dyes include methylene blue (MB), crystal violet (CV) and neutral red (NR). In addition, 1-4 have excellent characteristics that can reduce Cr(VI) to Cr(III) by photocatalytic technology. Within 30 min, the reduction rates were 95.85% for 1, 93.99% for 2, 90.29% for 3 and 88.18% for 4.

A series of isopolymolybdate-viologen hybrids with photo-, thermo- and electro-chromic properties.

The combination of electron-deficient viologen ligands with electron-rich POMs is a typical acceptor-donor system that has recently received much attention. Under solvothermal and hydrothermal conditions, by introducing three symmetric viologen ligands into POM-based hybrid materials, we successfully constructed four POMs-viologen inorganic-organic hybrid compounds, namely (1,3-bcbpy)2·(δ-Mo8O26) (1) (1,3-bcbpy·2Cl = 1,1'-bis(3-carboxybenzyl)-4,4'-bipyridine dichloride), {CoII(1,4-bcbpy)2(H2O)2[H2(ß-Mo8O26)]}·2H2O·2CH2O (2), (1,4-bcbpy)2·(δ-Mo8O26)·2H2O (3) (1,4-bcbpy·2Cl = 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridine dichloride, CH2O = formaldehyde), and {CuII(1,1-pmbby)2(H2O)[H2(ß-Mo8O26)2]}·5H2O·C2H7N (4) (1,1-pmbby·2Cl = 1,1'-[1,4-phenylbis(methylene)]bis-(4,4'-bipyridine)dichloride, C2H7N = dimethylamine). These four compounds exhibit different fascinating structures, especially compound 4 is a typical metal-organic framework. Compounds 1-4 exhibit good discoloration behaviors under various external stimuli. For example, compounds 1-4 showed a positive response to the irradiation from a 300 W Xe lamp. When a positive voltage was applied to the ECD based on compounds 1-4, 1/2/3/4-ECD underwent a significant color conversion. What's more, compound 4 also showed obvious discoloration results after heating. In a word, 1-4 are multifunctional discoloration materials under different external stimuli. In addition, the coated filter paper prepared based on compound 3 can be used as a new printing material medium and can be successfully applied in erasable inkless printing and dual anti-counterfeiting.

Hierarchical CoS2/MoS2 flower-like heterostructured arrays derived from polyoxometalates for efficient electrocatalytic nitrogen reduction under ambient conditions.

Electrochemical nitrogen reduction reaction (NRR) has been identified as a prospective alternative for sustainable ammonia production. Developing cost-effective and highly efficient electrocatalysts is critical for NRR under ambient conditions. Herein, the hierarchical cobalt-molybdenum bimetallic sulfide (CoS2/MoS2) flower-like heterostructure assembled from well-aligned nanosheets has been easily fabricated through a one-step strategy. The efficient synergy between different components and the formation of heterostructure in CoS2/MoS2 nanosheets with abundant active sites makes the non-noble metal catalyst CoS2/MoS2 highly effective in NRR, with a high NH3 yield rate (38.61 µg h-1 mgcat.-1), Faradaic efficiency (34.66%), high selectivity (no formation of hydrazine) and excellent long-term stability in 1.0 mol L-1 K2SO4 electrolyte (pH = 3.5) at -0.25 V versus the reversible hydrogen electrode (vs. RHE) under ambient conditions, exceeding much recently reported cobalt- and molybdenum-based materials, even catch up with some noble-metal-based catalyst. Density functional theory (DFT) calculation indicates that the formation of N2H* species on CoS2(200)/MoS2(002) is the rate-determining step via both the alternating and distal pathways with the maximum ΔG values (1.35 eV). These results open up opportunities for the development of efficient non-precious bimetal-based catalysts for NRR.

Fe Foam-Supported FeS2-MoS2 Electrocatalyst for N2 Reduction under Ambient Conditions.

Highly efficient catalysts with enough selectivity and stability are essential for electrochemical nitrogen reduction reaction (e-NRR) that has been considered as a green and sustainable route for synthesis of NH3. In this work, a series of three-dimensional (3D) porous iron foam (abbreviated as IF) self-supported FeS2-MoS2 bimetallic hybrid materials, denoted as FeS2-MoS2@IFx, x = 100, 200, 300, and 400, were designed and synthesized and then directly used as the electrode for the NRR. Interestingly, the IF serving as a slow-releasing iron source together with polyoxomolybdates (NH4)6Mo7O24·4H2O as a Mo source were sulfurized in the presence of thiourea to form self-supported FeS2-MoS2 on IF (abbreviated as FeS2-MoS2@IF200) as an efficient electrocatalyst. Further material characterizations of FeS2-MoS2@IF200 show that flower cluster-like FeS2-MoS2 grows on the 3D skeleton of IF, consisting of interconnected and staggered nanosheets with mesoporous structures. The unique 3D porous structure of FeS2-MoS2@IF together with synergy and interface interactions of bimetallic sulfides would make FeS2-MoS2@IF possess favorable electron transfer tunnels and expose abundant intrinsic active sites in the e-NRR. It is confirmed that synthesized FeS2-MoS2@IF200 shows a remarkable NH3 production rate of 7.1 ×10-10 mol s-1 cm-2 at -0.5 V versus the reversible hydrogen electrode (vs RHE) and an optimal faradaic efficiency of 4.6% at -0.3 V (vs RHE) with outstanding electrochemical and structural stability.