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The design of efficient catalysts for photocatalytic CO 2 conversion is of great importance for the sustainable development of society. Herein, three polyoxometalate (POM)-based crystalline materials were formulated prepared by substituting transition metals and adjusting solvent acidity with 2-(2-pyridyl) benzimidazole (pyim) as the light-trapping ligand, namely {[SiW 12 O 40 ][Co(pyim) 2 ] 2 }·2C 2 H 5 OH (SiW12Co2), {[SiW 12 O 40 ][Ni(pyim) 2 ] 2 }·2C 2 H 5 OH (SiW12Ni2), and {[SiW 12 O 40 ][Mn(pyim) 2 ] 2 }·2C 2 H 5 OH (SiW12Mn2). X-ray crystallography diffraction analysis indicates that the three complexes exhibit isostructural properties, and form a stable one-dimensional chain structure stabilized by two [M(pyim) 2 ] 2 2+ (M = Co, Ni, and Mn) fragments serving as dual-nodes to the adjacent SiW 12 units. A comprehensive analysis of the structural characterization and photocatalytic CO 2 reduction properties is presented. Under light irradiation, SiW12Co2 exhibited a remarkable CO generation rate of 10 733 μmol g -1 h -1 with a turnover number of 328, outperforming most of the reported heterogeneous POM-based photocatalysts. Besides, cycling tests revealed that SiW12Co2 is an efficient and stable photocatalyst with great recyclability for at least four successive runs. This study proves that the successful incorporation of diverse transition metals into the POM anion could facilitate the development of highly efficient photocatalysts for the CO 2 RR.

The anionic template method is an effective strategy for synthesizing high-nuclearity transition-lanthanide (3d-4f) heterometallic clusters. Herein, two lanthanide clusters with formulas [Gd 20 Ni 21 (μ 3 -OH) 21 (CO 3 ) 6 (IDA) 21 (C 2 H 4 NO 2 ) 6 (C 2 O 4 ) 3 (MoO 4 ) 1.5 (μ 2 -OH) 1.5 (H 2 O) 9 ]Cl 10.5 ·79H 2 O (1) and [Tb 20 Ni 21 (μ 3 -OH) 21 (CO 3 ) 6 (IDA) 21 (C 2 H 4 NO 2 ) 6 (C 2 O 4 ) 3 (MoO 4 )(μ 2 -OH) 2 (H 2 O) 10 ]Cl 11 ·32H 2 O (2) were synthesized by introducing MoO 4 2- anions as templates. Structural analysis indicates that compounds 1 and 2 are isomorphic, featuring a fascinating triangular-shaped metal framework. Magnetic property investigations illuminate the fact that compound 1 exhibits a large -Δ S m of 37.83 J kg -1 K -1 at 3 K for Δ H = 7 T. In particular, it is worth mentioning that compound 1 has an excellent low-field magnetic entropy (-Δ S m = 23.85 J kg -1 K -1 at 2 K, 2 T).

Two polyoxometalate (POM)-based hybrid compounds have been successfully designed and constructed by the hydrothermal method with molecular formulas [K(H 2 O) 2 FeII0.33Co 0.67 (H 2 O) 2 (DAPSC)] 2 {[FeII0.33Co 0.67 (H 2 O)(DAPSC)] 2 [FeII0.33Co 0.67 (H 2 O) 4 ] 2 [Na 2 FeIII4P 4 W 32 O 120 ]}·21.5H 2 O (1), and [Na(H 2 O) 2 FeII0.33Mn 0.67 (H 2 O) 2 (DAPSC)] 2 {[FeII0.33Mn 0.67 (H 2 O)(DAPSC)] 2 [FeII0.33Mn 0.67 (H 2 O) 4 ] 2 [Na 2 FeIII4P 4 W 32 O 120 (H 2 O) 2 ]}·24H 2 O (2) (DAPSC = 2,6-diacetylpyridine bis-(semicarbazone)), respectively. Structural analysis revealed that 1 and 2 consisted of metal-organic complexes containing DAPSC ligands with dumbbell-type inorganic clusters, iron-cobalt (iron-manganese) and some other ions. By utilizing a combination of strongly reducing {P 2 W 12 } units and bimetal-doped centres the CO 2 photoreduction catalytic capacity of 1 and 2 was improved. Notably, the photocatalytic performance of 1 was much better than that of 2. In CO 2 photoreduction, 1 exhibited CO selectivity as high as 90.8%. Furthermore, for 1, the CO generation rate reached 6885.1 μmol g -1 h -1 at 8 h with 3 mg, and its better photocatalytic performance was presumably due to the introduction of cobalt and iron elements to give 1 a more appropriate energy band structure. Further recycling experiments indicated that 1 was a highly efficient CO 2 photoreduction catalyst, which could still possess catalytic activity after several cycles.

The self-assembly of the high-nuclearity Ln-exclusive nanoclusters is challenging but of significance due to its aesthetically pleasing architectures and far-reaching latent applications in magnetic cooling technologies. Herein, two novel high-nuclearity lanthanide nanoclusters were successfully synthesized under solvothermal conditions, formulated as {[Gd 18 (IN) 20 (HCOO) 8 (μ 6 -O)(μ 3 -OH) 24 (H 2 O) 4 ]·4H 2 O} n and {[Eu 18 (IN) 16 (HCOO) 8 (CH 3 COO) 4 (μ 6 -O)(μ 3 -OH) 24 (H 2 O) 4 ]·5H 2 O} n (abbreviated as Gd 18 and Eu 18 , HIN = isonicotinic acid). Both of them possess novel and exquisite windmill-shaped cationic cores in the family of high-nuclearity Ln-exclusive nanoclusters. Remarkably, the adjacent second building units are interconnected into a three-dimensional (3D) metal-organic framework by IN - ligands. As expected, the abundant existence of Gd III ions endows Gd 18 with a favorable magnetic entropy change at 2.0 K for Δ H = 7.0 T (-Δ S m max = 40.0 J kg -1 K -1 ), and Eu 18 displays the typical luminescence of Eu III ions.

Sulfur oxides from the combustion of petrol and excessive emissions of carbon dioxide (CO 2 ) are currently the main causes of environmental pollution. Considerable interest has been paid to solving the challenge, and catalytic reactions seem to be the desired choice. Due to the high density of Lewis acid active sites, polyoxometalates are considered to be the ideal choice for these catalytic reactions. Herein, two captivating polyoxometalate-based metal-organic complexes, formulated as [Co(H 2 O) 2 DABT] 2 [CrMo 6 (OH) 5 O 19 ] ( {Co-CrMo 6 } ) and [Zn(H 2 O) 2 DABT] 2 [CrMo 6 (OH) 5 O 19 ] ( {Zn-CrMo 6 } ) (DABT = 3,3'-diamino-5,5'-bis(1 H -1,2,4-triazole)) were successfully obtained under hydrothermal conditions. The structural analysis demonstrates that {Co-CrMo 6 } and {Zn-CrMo 6 } are isostructural with two different transition metal (Co/Zn) ions based on quadridentate Anderson-type [CrMo 6 (OH) 5 O 19 ] 4- polyanions. A fan-shaped unit of {Co-CrMo 6 } / {Zn-CrMo 6 } is linked to generate a one-dimensional (1D) ladder-like structure. Intriguingly, benefitting from rich Co centers with a suitable energy band structure, {Co-CrMo 6 } displays better photocatalytic activity than {Zn-CrMo 6 } for converting CO 2 into CO, endowing the CO formation of 1935.3 μmol g -1 h -1 with high selectivity. Meanwhile, {Co-CrMo 6 } also exhibits a satisfactory removal rate of 99% for oxidizing dibenzothiophene at 50 °C, which suggests that {Co-CrMo 6 } may be utilized as a potential dual functional material with immense prospects in photocatalytic CO 2 reduction and sulfur oxidation for the first time.

Carbon dioxide (CO 2 ) and the combustion of sulfide in gasoline are the main causes of air pollution. A great deal of attention has been paid to solving the problem and the catalytic reaction seems to be a decent choice. Due to the high-density of Lewis acidic active sites, polyoxometalates are undoubtedly an ideal choice for the sulfur oxidation reaction. With the reasons foregoing, two novel Zn-capped polyoxometalate-based organic-inorganic hybrids, {[α-PMoV2MoVI10O 39 (OH)Zn 2 ][bbbm] 3 }·0.5C 2 H 5 OH (1) and TBA 2 {[ε-PMoV8MoVI4O 37 (OH) 3 Zn 4 ][phim] 3 } (2) ((where bbbm = 1-(4-imidazol-1-ylbutyl) imidazole) and phim = 2-phenylimidazole) were successfully obtained by hydrothermal synthesis. In the two compounds, the N-donor ligands in a monodentate or bidentate coordination mode are directly connected to the Keggin anions by Zn-capped atoms, forming an extended one-dimensional chain. It is noteworthy that compound 2 ends up with an interesting spiral infinite chain possibly thanks to the TBA + cations residing in gaps as structure-directing agents. Simultaneously, the catalytic properties indicate that compounds 1 and2 as efficient heterogeneous catalysts display a decent catalytic activity in the sulfur removal process. Especially, 2 enabled satisfying catalytic oxidation of dibenzothiophene (DBT) to produce more valuable dibenzothiophene sulfone (DBTO 2 ) at 55 °C, and the conversion almost reached 99%. Besides, compound 2 also shows satisfactory catalytic effectiveness in the oxidation of various epoxides in the CO 2 cycloaddition reaction, which suggests that compound 2 has the potential to function as a dual functional material with tremendous prospects in sulfur oxidation and carbon dioxide cycloaddition for the first time.

Designing and synthesizing lanthanide clusters have always been a research hotspot. Herein, three lanthanide clusters with the formula [Ln 8 (IN) 14 (μ 3 -OH) 8 (μ 2 -OH) 2 (H 2 O) 8 ]· x H 2 O (Ln = 1-Gd and x = 11; Ln = 2-Dy and x = 8; Ln = 3-Eu and x = 8) have been isolated in the presence of isonicotinic acid under solvothermal conditions. Structural analysis indicates that those three compounds are isostructural, featuring boat-shaped {Ln 8 } metal frameworks. Magnetic measurements reveal that 1-Gd exhibits a larger MCE with the maximum -Δ S m value of 31.77 J kg -1 K -1 at 2 K for Δ H = 7 T, while 2-Dy displays slow magnetization relaxation. Besides, the photoluminescence properties of 3-Eu were investigated.

Two captivating {P4Mo6}-based compounds, formulated as (H2bbi)2{[Co2(bbi)][Co2.33(H2O)4][H9.33CoP8Mo12O62]}·4H2O (1) and (H2bbi){[Zn(Hbbi)]2[Zn0.75(bbi)][K2Zn(H2O)4][H8.5ZnP8Mo12O62]} (2) [bbi = 1,1'-(1,4-butanediyl)bis(imidazole)], were successfully synthesized under hydrothermal conditions. Structural analysis demonstrates that compounds 1 and 2 are constructed from hourglass-shaped structures [M(P4Mo6O31)2]n- (M = Co, Zn), which are all made up of molybdophosphates and one transition metal ion as the central connecting node. Compounds 1 and 2 feature three-dimensional (3D) frameworks, which are all connected to form a 3D structure by metal ions and bbi ligands. More interestingly, compound 1 exhibits higher catalytic activity than 2 in CO2 photoreduction due to the suitable energy band structure of Co species in {P4Mo6} clusters. The CO yield was 3261 μmol g-1 with high selectivity in 8 h for compound 1 in photocatalytic CO2 reduction, which is highly promising in the photocatalytic field. Additionally, the photoluminescence properties of 2 were investigated.

Objective: To evaluate the treatment of open Pilon fractures., Methods: A total of 126 open Pilon fracture cases were reviewed retrospectively. The patients were treated from February 1996 to March 2009, included 72 males and 54 females with an average age of 36 years old ranging from 17 to 65 years. According to the Ruedi-Augower classification, there were 28 cases of type I, 58 of type II, and 40 of type III. Among all the cases, 31 cases were treated with external fixators combined with limited internal fixations, 80 cases were treated with open reduction and internal fixation with anatomical plates, 15 cases with open reduction and cross K-wire fixations., Results: All cases were followed-up for from 10 to 26 months with an average of 16 months. The average bone healing time was 10 weeks (from 8 to 14 weeks). According to the Mazur ankle function evaluation, the results were excellent in 89 cases, good in 26,fair in 9,poor in 2. The excellent and good rate was 91.2%., Conclusion: The "Personalized treatment principle" effectively prevents the occurrence of complications and helps to restore the joint functions.