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Two isostructural MOFs with coordination of different halogen ions (Cl- and Br-), namely NNU-17 and NNU-18, were utilized to reveal the influence of different electron-withdrawing halogen anions on ECR performance. The performance difference between them mainly originates from the different abilities of adsorption and activation of CO2 by halogen ions.

Photo/electrocatalysis of water (H 2 O) splitting and CO 2 reduction reactions is a promising strategy to alleviate the energy crisis and excessive CO 2 emissions. For the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO 2 reduction reaction (CO 2 RR) involved, the development of effective photo/electrocatalysts is critical to reduce the activation energy and accelerate the sluggish dynamics. Polyoxometalate (POM)-based compounds with tunable compositions and diverse structures are emerging as unique photo/electrocatalysts for these reactions as they offer unparalleled advantages such as outstanding solution and redox stability, quasi-semiconductor behaviour, etc. This Minireview provides a basic introduction related to photo/electrocatalytic HER, OER and CO 2 RR, followed by the classification of pristine POM-based compounds toward different catalytic reactions. Recent breakthroughs in engineering POM-based compounds as efficient photo/electrocatalysts are highlighted. Finally, the advantages, challenges, strategies and outlooks of POM-based compounds on improving photo/electrocatalytic performance are discussed., (© 2020 Wiley-VCH GmbH.)

Metal-organic framework (MOF) based mixed matrix membranes (MMMs) have received significant attention in applications such as gas separation, sensing, and energy storage. However, the mass production of MOF-based MMMs with retained porosity remains a longstanding challenge. Herein, an in situ heat-assisted solvent-evaporation method is described to facilely produce MOF-based MMMs. This method can be extended into various MOFs and polymers with minimum reaction time of 5 min. Thus-obtained MMMs with high uniformity, excellent robustness, well-tuned loading, and thickness can be massively produced in industrial-level efficiency (≈4 m in a batch experiment). Furthermore, they can be readily applied as powerful separators for Li-S cell with high specific capacity (1163.7 mAh g -1 ) and a capacity retention of 500.7 mAh g -1 after 700 cycles at 0.5 C (0.08% fading per cycle). This work may overcome the longstanding challenge of processing MOFs into MMMs and largely facilitate the industrialization process of MOFs., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by Wiley‐VCH GmbH.)

Electrochemical CO 2 reduction reaction (CO 2 RR) to formate is economically viable considering the energy input and market value. Through learning nature, a series of chloroplast-like porous bismuth-based core-shell (CPBC) materials have been designed. In these materials, the porous carbon can enrich and transfer CO 2 to the core-shell Bi@Bi 2 O 3 in CO 2 reduction process, during which Bi 2 O 3 layer can be transformed into activated metastable layer to efficiently convert CO 2 into formate and Bi can provide abundant electrons. Based on this, superior performances for most of important parameters in CO 2 RR can be achieved and best of them, CPBC-1 presents remarkable Faradaic efficiency (FE formate  > 94%) over a wide potential range (-0.65 to -1.0 V) with high catalysis durability (>72 h). Noteworthy, its maximum energy efficiency is as high as 76.7% at -0.7 V, the highest one in reported bismuth-based materials. This work opens novel perspectives in designing nature-inspired CO 2 RR electrocatalysts., (Copyright © 2020 Science China Press. Published by Elsevier B.V. All rights reserved.)

Based upon the hetero-N,O ligand of pyrimidine-5-carboxylic acid (Hpmc), a new semiconductive Cu(i)/Cu(ii) mixed-valence MOF with the full light spectrum and a novel topology of {4 3 ·6 12 ·8 6 } 2 {4 3 ·6 3 } 2 {6 3 } 6 {6 4 ·8 2 } 3 , {(Cu 4 I 4 ) 2.5 [Cu 3 (μ 4 -O) (μ 3 -I) (pmc) 3 (Dabco) 3 ]·2.5DMF·2MeCN} ∞ (NJU-Bai61, NJU-Bai for Nanjing University Bai group; Dabco = 1,4-diazabicyclo [2.2.2] octane), was synthesized stepwise. NJU-Bai61 exhibits good water/pH stabilities and a relatively large CO 2 adsorption capacity (29.82 cm 3 g -1 at 1 atm, 273 K) and could photocatalyze the reduction of CO 2 into CH 4 without additional photosensitizers and cocatalysts and with a high CH 4 production rate (15.75 μmol g -1 h -1 ) and a CH 4 selectivity of 72.8%. The CH 4 selectivity is the highest among the reported MOFs in aqueous solution. Experimental data and theoretical calculations further revealed that the Cu 4 I 4 cluster may adsorb light to generate photoelectrons and transfer them to its Cu 3 OI(CO 2 ) 3 cluster, and the Cu 3 OI(CO 2 ) 3 cluster could provide active sites to adsorb and reduce CO 2 and deliver sufficient electrons for CO 2 to produce CH 4 . This is the first time that the old Cu(i) x X y L z coordination polymers' application has been extended for the photoreduction of CO 2 to CH 4 and this opens up a new platform for the effective photoreduction of CO 2 to CH 4 ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Identification of the real catalytic site in CO 2 reduction reaction (CO 2 RR) is critical for the rational design of catalysts and the understanding of reactive mechanisms. In this study, the catalytic activity of pyridine-containing materials was for the first time structurally demonstrated in CO 2 RR by crystalline supramolecular coordination compounds model system. The system consists of three stable supramolecular coordination compounds (Ni-TPYP, Ni-TPYP-1 and Ni-TPP) with different numbers (4, 2 and 0) of active pyridine groups (i.e. uncoordinated pyridine nitrogen atoms). The electrocatalytic test results show that with the decrease of the number of active pyridine groups, the CO 2 RR performance is gradually reduced, mainly showing the reduction of highest FE CO (99.8%, 83.7% and 25.6%, respectively). The crystallographic, experimental and theoretical evidences prove that the CO 2 RR activity is more likely derived from uncoordinated pyridine nitrogen than the electrocatalytic inert metal nickel in porphyrin center. This work serves as an important case study for the identification of electrocatalytic activity of pyridine-containing materials in CO 2 RR by simple supramolecular model system., (© The Author(s) 2020. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

Aim: To quantitatively evaluate the effect of the combined use of 577-nm subthreshold micropulse macular laser (SML) and multi-point mode pan retinal laser photocoagulation (PRP) on severe non-proliferative diabetic retinopathy (NPDR) with central-involved diabetic macular edema (CIDME) using optical coherence tomography angiography (OCTA)., Methods: In this observational clinical study, 86 eyes of 86 NPDR patients with CIDME who underwent SML and PRP treatment were included. Images were obtained 1d before laser and post-laser (1d, 1wk, 1, 3, and 6mo) using AngioVue software 2.0. Best corrected visual acuity (BCVA, LogMAR), foveal avascular zone area (FAZ), choriocapillary flow area (ChF), parafoveal vessel density (PVD), capillary density inside disc (CDD), peripapillary capillary density (PCD), macular ganglion cell complex thickness (mGCCT), central macular thickness (CMT), and subfoveal choroidal thickness (ChT) were compared between pre- and post-laser treatment., Results: BCVA remained stable during 6mo post-laser therapy (pre-laser vs 6mo post-laser: 0.53±0.21 vs 0.5±0.15, P >0.05). PVD, ChF, ChT, CMT, and mGCCT significantly increased 1d post-laser therapy [pre-laser vs 1d post-laser: superficial PVD (%), 40.51±3.42 vs 42.43±4.68; deep PVD (%), 42.66±3.67 vs 44.78±4.52; ChF, 1.72±0.21 vs 1.9±0.12 mm 2 ; ChT, 302.45±69.74 vs 319.38±70.93 µm; CMT, 301.65±110.78 vs 320.86±105.62 µm; mGCCT, 105.71±10.72 vs 115.46±9.64 µm; P <0.05]. However, PVD, ChF and ChT decreased to less than baseline level at 6mo post-laser therapy (pre-laser vs 6mo post-laser: superficial PVD (%), 40.51±3.42 vs 36.32±4.19; deep PVD (%), 42.66±3.67 vs 38.76±3.74; ChF, 1.72±0.21 vs 1.62±0.09 mm 2 ; ChT, 302.45±69.74 vs 289.61±67.55 µm; P <0.05), whereas CMT and mGCCT decreased to baseline level at 6mo post-laser therapy (CMT, 301.65±110.78 vs 297.77±90.23 µm; mGCCT, 105.71±10.72 vs 107.05±11.81 µm; P >0.05). Moreover, FAZ continuously increased while CDD and PCD continuously decreased in 6mo after laser therapy. CMT and ChT had a significant positive correlation with ChF and PVD in most post-laser stages., Conclusion: During a 6-month follow-up period after combined use of SML and PRP therapy, BCVA remained stable and there was a decreased trend in macular edema. Blood flow increased at 1d post-laser therapy and reduced at 6mo post-laser therapy., (International Journal of Ophthalmology Press.)

The synthesis of hollow opening polyhedral cages has always been an attractive but challenging goal, especially with regard to inorganic polyhedral cages. Herein, we present a novel, 240-nuclearity giant polymolybdate cage prepared via hydrothermal synthesis. This cage is composed of 20 tripod-shaped [Mo 6 O 22 (SO 3 )] n - /[Mo 6 O 21 (SO 4 )] n - building blocks with three connected vertices and 30 cubane-type [Mo 4 O 16 ] n - edge building blocks, featuring a rare, nearly regular pentagonal dodecahedron with a large inner cavity (diameter up to 1.8 nm) and 12 opening pentagonal windows. This is the highest nuclearity hollow opening dodecahedral cage reported to date. Importantly, this cage exhibits good stability in solution, as revealed by scanning transmission electron microscopy (STEM), TEM, UV-vis, and Raman spectra. In addition, the bulk sample of this compound exhibits an ultrahigh proton conductivity of 1.03 × 10 -1 S cm -1 at 80 °C and 98% relative humidity, which is the highest among polyoxometalate-based crystalline proton conductors.

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic-inorganic Z-scheme heterojunctions for artificial photosynthesis is presented. A series of COF-semiconductor Z-scheme photocatalysts combining water-oxidation semiconductors (TiO 2 , Bi 2 WO 6 , and α-Fe 2 O 3 ) with CO 2 reduction COFs (COF-316/318) was synthesized and exhibited high photocatalytic CO 2 -to-CO conversion efficiencies (up to 69.67 μmol g -1  h -1 ), with H 2 O as the electron donor in the gas-solid CO 2 reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic-semiconductor systems utilizing the Z-scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor-to-COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO 2 reduction and holes in the semiconductor for H 2 O oxidation, thus mimicking natural photosynthesis., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of stable heterometallic Fe 2 M cluster-based MOFs (NNU-31-M, M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO 2 and H 2 O into HCOOH and O 2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low-valent metal M accepts electrons to reduce CO 2 , and high-valent Fe uses holes to oxidize H 2 O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU-31-Zn exhibits the highest HCOOH yield of 26.3 μmol g -1  h -1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Efficient conversion of carbon dioxide (CO 2 ) into value-added products is essential for clean energy research. Design of stable, selective, and powerful electrocatalysts for CO 2 reduction reaction (CO 2 RR) is highly desirable yet largely unmet. In this work, a series of metalloporphyrin-tetrathiafulvalene based covalent organic frameworks (M-TTCOFs) are designed. Tetrathiafulvalene, serving as electron donator or carrier, can construct an oriented electron transmission pathway with metalloporphyrin. Thus-obtained M-TTCOFs can serve as electrocatalysts with high FE CO (91.3%, -0.7 V) and possess high cycling stability (>40 h). In addition, after exfoliation, the FE CO value of Co-TTCOF nanosheets (~5 nm) is higher than 90% in a wide potential range from -0.6 to -0.9 V and the maximum FE CO can reach up to almost 100% (99.7%, -0.8 V). The electrocatalytic CO 2 RR mechanisms are discussed and revealed by density functional theory calculations. This work paves a new way in exploring porous crystalline materials in electrocatalytic CO 2 RR.

Photocatalytic CO 2 reduction into energy carriers is of utmost importance due to the rising concentrations of CO 2 and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH 4 ), from CO 2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H 2 TCPP) linkers, exhibiting high selectivity (>96%) for CH 4 formation in a photocatalytic CO 2 -reduction system. To our knowledge, the high CH 4 selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO 2 -to-CH 4 conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH 4 formation, considering that eight Mo V atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO 2 -to-CH 4 transformation., (© The Author(s) 2019. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

The energy crisis and environmental pollution have forced scientists to explore alternative energy conversion and storage devices. The anodic reactions of these devices are all oxygen evolution reactions (OER), so the development of efficient OER electrocatalysts is of great significance. At the same time, understanding the reaction mechanism of OER is conducive to the rational design of efficient OER electrocatalysts. In general, catalytic active centers play a direct role in OER performance. In this paper, a series of stable bimetallic metal-organic frameworks (MOFs, named as Fe 3 -Co n -X 2 , n=2, 3 and X=F, Cl, Br) with similar structure were synthesized by changing the halogen coordinated with the cobalt metal active center, aiming to investigate the influence of halogen substitution effect on OER performance. It was found that the OER activity of Fe 3 -Co 3 -F 2 is much better than Fe 3 -Co 2 -Cl 2 and Fe 3 -Co 2 -Br 2 , indicating that the regulation of the electronegativity change of the coordination halogen atom can regulate the coordination electron structure of the metal active center, thereby achieving effective regulation of OER performance., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the past 200 years, the most famous and important heteroatom Keggin architecture in polyoxometalates has only been synthesized with Mo, W, V, or Nb. Now, the self-assembly of two phosphate (PO 4 3- )-centered polyoxo-titanium clusters (PTCs) is presented, PTi 16 and PTi 12 , which display classic heteroatom Keggin and its trivacant structures, respectively. Because Ti IV has lower oxidate state and larger ionic radius than Mo VI , W VI , V V , and Nb V , additional Ti IV centres in these PTCs are used to stabilize the resultant heteroatom Keggin structures, as demonstrated by the cooresponding theoretical calculation results. These photoactive PTCs can be utilized as efficient photocatalysts for highly selective CO 2 -to-HCOOH conversion. This new discovery indicates that the classic heteroatom Keggin family can be assembled with Ti, thus opening a research avenue for the development of PTC chemistry., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reticular chemistry has been an important guiding principle for the design of metal-organic frameworks (MOFs). This approach utilizes discrete building units (molecules and clusters) that are connected through strong bonds into extended networks assisted by topological considerations. Although the simple design principle of connecting points and lines has proved successful, new design strategies are still needed to further explore the structures and functions of MOFs. Herein, we report the design and synthesis of two mixed-ligand MOFs, [(CH 3 ) 2 NH 2 ] 4 [Zn 4 O] 4 [Zn(TCPP)] 5 [BTB] 8/3 (PCN-137) and [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 ][TCPP][TBTB] 8/3 (PCN-138) (BTB = 1,3,5-benzene(tris)benzoate, TBTB = 4,4',4″-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoate, and TCPP = tetrakis(4-carboxyphenyl)porphyrin) by the stacking of face-sharing Archimedean solids. In these two MOFs, high-symmetrical metal clusters serve as vertices, and tritopic or tetratopic carboxylate ligands function as triangular and square faces, leading to the formation of two kinds of Archimedean solids (rhombicuboctahedron and cuboctahedron). Furthermore, the ordered accumulation of Archimedean solids successfully gives rise to 3D structures through face-sharing, highlighting the polyhedron-based approach for the design and preparation of MOFs. In addition, PCN-138 was utilized as a heterogeneous catalyst toward CO 2 photoreduction under visible-light irradiation. This structure shows high photocatalytic activity, which can be attributed to the coexistence of photosensitizing porphyrin fragments and Zr-oxo centers within the PCN-138 scaffold.

Solar energy-driven conversion of CO 2 into fuels with H 2 O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO 2 with H 2 O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO 2 reduction and H 2 O oxidation. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H 2 O oxidation to O 2 . Furthermore, DFT calculations combined with a crystal structure model confirmed the structure-function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Embedding cubane [M 4 (OH) 4 ] (M=Ni, Co) clusters within the matrix of metal-organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore-space partition of the cubic primitive minimal-surface net (MOF-14-type) has been realized. CTGU-15 made from the [Ni 4 (OH) 4 ] cluster not only has very high BET surface area (3537 m 2  g -1 ), but also exhibits bi-microporous features with well-defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU-15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU-15 (1:2) made from ketjen black (KB) and CTGU-15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg -1 and excellent peak current density (29.8 mA cm -2 ) at low potential (0.6 V). The isostructural cobalt structure (CTGU-16) has also been synthesized, further expanding the application potential of this material type., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel polyoxometalate (POM)-based metal-organic framework, TBA 5 [P 2 Mo 16 V Mo 8 VI O 71 (OH) 9 Zn 8 (L) 4 ] ( NNU-29 ), was in situ synthesized and applied into CO 2 photoreduction. The selection of porous material containing a reductive POM cluster is considered to be helpful for CO 2 reduction; meanwhile, a hydrophobic-group-modified organic ligand enables NNU-29 to exhibit good chemical stability and restrains hydrogen generation to some extent. In the photocatalytic CO 2 reduction, the yield of HCOO - reached 35.2 μmol in the aqueous solution with selectivity of 97.9% after 16 h.

In order to explore novel colorimetric biosensors with high sensibility and selectivity, two new Keggin polyoxometalates (POMs)-based Cu-trz (1,2,4-triazole) metal-organic frameworks (MOFs) with suitable specific surface areas and multiple active sites were favorably fabricated; then single-walled carbon nanotubes (SWNTs) were merged with new POMOFs to construct POMOF/SWNT nanocomposites. Herein, POMOF/SWNT nanocomposites as peroxidase mimics were explored for the first time, and the peroxidase-mimicking activity of the prepared POMOF/SWNT nanocomposites is heavily dependent on the mass ratio of POMOFs and SWNTs, in which the maximum activity is achieved at the mass ratio of 2.5:1 (named PMNT-2). More importantly, PMNT-2 exhibits the lowest limit of detection (0.103 μM) among all reported materials to date and the assumable selectivity toward l-cysteine (l-Cys) detection. With these findings, a convenient, sensitive, and effective "on-off switch" colorimetric platform for l-Cys detection has been successfully developed, providing a promising prospect in the biosensors and clinical diagnosis fields.

Visible-light driven photoconversion of CO 2 into energy carriers is highly important to the natural carbon balance and sustainable development. Demonstrated here is the adenine-dependent CO 2 photoreduction performance in green biomimetic metal-organic frameworks. Photocatalytic results indicate that AD-MOF-2 exhibited a very high HCOOH production rate of 443.2 μmol g -1  h -1 in pure aqueous solution, and is more than two times higher than that of AD-MOF-1 (179.0 μmol g -1 h -1 ) in acetonitrile solution. Significantly, experimental and theoretical evidence reveal that the CO 2 photoreduction reaction mainly takes place at the aromatic nitrogen atom of adenine molecules through a unique o-amino-assisted activation rather than at the metal center. This work not only serves as an important case study for the development of green biomimetic photocatalysts used for artificial photosynthesis, but also proposes a new catalytic strategy for efficient CO 2 photoconversion., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The aim of this retrospective analysis was to evaluate the efficacy and toxicity of combination chemotherapy with paclitaxel, 5-fluorouracil, and leucovorin (TFL) as first-line treatment in patients with advanced gastric cancer (AGC). One hundred and thirteen patients were enrolled in the study who were confirmed to have AGC by histopathology. These patients were treated with TFL: paclitaxel at a dose of 135 mg/m as a 3-h intravenous infusion on day 1, LV 400 mg/m as an intravenous infusion over 2 h on day 1, followed by 5-fluorouracil 2400 mg/m as an infusion over a 46-h period on 3 consecutive days. Cycles were repeated every 2 weeks. A total of 113 patients were assessed for their response to therapy. A total of three patients achieved complete responses and 46 patients achieved partial responses, yielding an overall objective response rate of 43.4% [95% confidence interval (CI): 34.3-52.5%]. Fifty-four cases of stable disease and 10 cases of progressive disease were observed in the remaining patients. The median time to progression and overall survival were 5.2 months (95% CI: 4.7-5.8 months) and 14.1 months (95% CI: 12.5-15.8 months), respectively. Toxicities were tolerable and moderate. The most common grade 3-4 toxicities included leukopenia (16.8%), neutropenia (17.7%), anemia (8.0%), thrombocytopenia (5.3%), and fatigue (6.2%). Combination chemotherapy with TFL offers an active and safe therapeutic approach for patients with AGC.

As one class of important functional materials, transition metal phosphides (TMPs) nanostructures show promising applications in catalysis and energy storage fields. Although great progress has been achieved, phase-controlled synthesis of cobalt phosphides nanocrystals or related nanohybrids remains a challenge, and their use in overall water splitting (OWS) is not systematically studied. Herein, three kinds of cobalt phosphides nanocrystals encapsulated by P-doped carbon (PC) and married with P-doped graphene (PG) nanohybrids, including CoP@PC/PG, CoP-Co 2 P@PC/PG, and Co 2 P@PC/PG, are obtained through controllable thermal conversion of presynthesized supramolecular gels that contain cobalt salt, phytic acid, and graphene oxides at proper temperature under Ar/H 2 atmosphere. Among them, the mixed-phase CoP-Co 2 P@PC/PG nanohybrids manifest high electrocatalytic activity toward both hydrogen and oxygen evolution in alkaline media. Remarkably, using them as bifunctional catalysts, the fabricated CoP-Co 2 P@PC/PG||CoP-Co 2 P@PC/PG electrolyzer only needs a cell voltage of 1.567 V for driving OWS to reach the current density at 10 mA cm -2 , superior to their pure-phase counterparts and recently reported bifunctional catalysts based devices. Also, such a CoP-Co 2 P@PC/PG||CoP-Co 2 P@PC/PG device exhibits outstanding stability for OWS. This work may shed some light on optimizing TMPs nanostructures based on phase engineering, and promote their applications in OWS or other renewable energy options., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polyoxometalates (POMs), which possess strong acidity and chemical stability, are promising solid proton conductors and potential candidates for proton exchange membrane fuel cell applications. To investigate how factors such as proton concentration and carrier affect the overall proton conduction, we have synthesized new compounds HImMo 132 (Im, imidazole), HMeImMo 132 , ILMo 132 , and TBAMo 132 with hollow structures and HImPMo 12 with a solid spherelike structure. These crystal models were prepared by encapsulating POM with organic molecules with different proton contents. Among them, the single-crystal sample of the hollow structure HImMo 132 containing more proton sources shows a high proton conductivity of 4.98 × 10 -2 S cm -1 , which was approximately 1 order of magnitude greater than that of the solid cluster HImPMo 12 with the same proton sources and 3 orders of magnitude greater than that of the proton-free organic cation-encapsulated giant ball TBAMo 132 . This study provides a theoretical guidance toward designing and developing new-generation proton conductors and studying their performances at the molecular level.

The incorporation of large π-conjugated ligands into metal-organic frameworks (MOFs) can introduce intriguing photophysical and electrochemical properties into the framework. However, these effects are often hindered by the strong π-π interaction and the low solubility of the arylated ligands. Herein, we report the synthesis of a porous zirconium-based MOF, Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6 (H 2 O) 6 (HCHC) (PCN-136, HCHC = hexakis(4-carboxyphenyl)hexabenzocoronene), which is composed of a hexacarboxylate linker with a π-conjugated hexabenzocoronene moiety. Direct assembly of the Zr 4+ metal centers and the HCHC ligands was unsuccessful due to the low solubility and the unfavorable conformation of the arylated HCHC ligand. Therefore, PCN-136 was obtained from aromatization-driven postsynthetic annulation of the hexaphenylbenzene fragment in a preformed framework (pbz-MOF-1) to avoid π-π stacking. This postsynthetic modification was done through a single-crystal-to-single-crystal transformation and was clearly observable utilizing single -crystal X-ray crystallography. The formation of large π-conjugated systems on the organic linker dramatically enhanced the photoresponsive properties of PCN-136. With isolated hexabenzocoronene moieties as photosensitizers and Zr-oxo clusters as catalytic sites, PCN-136 was employed as an inherent photocatalytic system for CO 2 reduction under visible-light irradiation, which showed increased activity compared with pbz-MOF-1.

Ozone-biological activated carbon (O 3 -BAC) was studied for the advanced removal of organics from micro-polluted source water in the water supply plant P located in J City in the Yangtze Delta Region. The results show that 19.2% of the permanganate index, 10.4% of total organic carbon, and 23.0% of UV 254 were removed by the advanced treatment of O 3 -BAC. Eight types of polycyclic aromatic hydrocarbon (PAH), 16 types of organochlorinated pesticides (OCPs), and five types of haloacetic acids (HAAs) were detected in the source water. The total concentrations were 53.9-100.0, 6.5-41.8, and 2.5×10 3 -1.1×10 4 ng·L -1 , respectively. The advanced O 3 -BAC treatment removed 32.5% of PAHs and 25.9% of OCPs, greatly improving the effluent of the conventional water supply process. However, HAAs were mainly removed with the conventional process, with a removal rate of 33.8%-87.0%. After the advanced treatment with O 3 -BAC, the amount of chloroacetic acid slightly decreased, while the concentration of bromoacetic acid slightly increased.

The anthropogenic volatile organic compounds (VOCs) emissions inventory in Jiaxing for 2015 was established by collecting comprehensive activity data of anthropogenic sources and adopting scientific and reasonable estimation methods and emissions factors. Results showed that the total VOCs emissions in Jiaxing for 2015 amounted to 10.21×10 4 t, of which 78.15%, 12.08%, 5.83%, 3.24%, 0.26%, and 0.44% was contributed by industrial sources, vehicles, domestic sources, oil storage and transport, waste disposal, and burning of agricultural crop residues, respectively. Packaging and printing industries, the surface coating industry, the dyeing industry, chemical materials manufacturers, and the petrochemical industry are the most important VOCs-emitting industries. Haining, Tongxiang, and Pinghu were the three cities with the highest emissions amounts, which contributed 50% of the total VOCs emissions. The average emissions intensity of VOCs in Jingkai, Haining, and Nanhu exceeded 30 t·km -2 .

The design of highly stable, selective and efficient electrocatalysts for CO 2 reduction reaction is desirable while largely unmet. In this work, a series of precisely designed polyoxometalate-metalloporphyrin organic frameworks are developed. Noted that the integration of {ε-PMo 8 V Mo 4 VI O 40 Zn 4 } cluster and metalloporphyrin endows these polyoxometalate-metalloporphyrin organic frameworks greatly advantages in terms of electron collecting and donating, electron migration and electrocatalytic active component in the CO 2 reduction reaction. Thus-obtained catalysts finally present excellent performances and the mechanisms of catalysis processes are discussed and revealed by density functional theory calculations. Most importantly, Co-PMOF exhibits remarkable faradaic efficiency ( > 94%) over a wide potential range (-0.8 to -1.0 V). Its best faradaic efficiency can reach up to 99% (highest in reported metal-organic frameworks) and it exhibits a high turnover frequency of 1656 h -1 and excellent catalysis stability ( > 36 h).

Photocatalytic hydrogen evolution technology is recognized as a promising approach to relieving the growing energy crisis. Therefore, the development of a stable high-performance photocatalyst has long been the focus of research. In this work, quaternary composite materials involving a snowflake-like CdS nanocrystal wrapped by different amounts of polyoxometalate-decorated g-C 3 N 4 and polypyrrole (GPP@CdS) have been synthesized as photocatalysts for hydrogen production under visible-light irradiation. It has been revealed that the best composite (40 % GPP@CdS composite) exhibits hydrogen production activity of 1321 μmol, which exceeds that of CdS by a factor of more than two, and can be used in at least seven cycles with negligible loss of activity. The enhanced photocatalytic performance has been primarily attributed to the efficient synergy of CdS, g-C 3 N 4 , polypyrrole (PPy), and the polyoxometalate Ni 4 (PW 9 ) 2 . It should be noted that the introduction of PPy and g-C 3 N 4 into the title composite simultaneously promotes electron/hole pair separation and photocatalytic stability, whereas Ni 4 (PW 9 ) 2 serves as an efficient electron modulator and extra catalytic active site., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The photocatalytic reduction of CO 2 to value-added methane (CH 4 ) has been a promising strategy for sustainable energy development, but it is challenging to trigger this reaction because of its necessary eight-electron transfer process. In this work, an efficient photocatalytic CO 2 -to-CH 4 reduction reaction was achieved for the first time in aqueous solution by using two crystalline heterogeneous catalysts, H{[Na 2 K 4 Mn 4 (PO 4 ) (H 2 O) 4 ]⊂{[Mo 6 O 12 (OH) 3 (HPO 4 ) 3 (PO 4 )] 4 [Mn 6 (H 2 O) 4 ]}·16H 2 O ( NENU-605 ) and H{[Na 6 CoMn 3 (PO 4 )(H 2 O) 4 ]⊂{[Mo 6 O 12 (OH) 3 (HPO 4 ) 3 (PO 4 )] 4 [Co 1.5 Mn 4.5 ]}·21H 2 O ( NENU-606 ). Both compounds have similar host inorganic polyoxometalate (POM) structures constructed with strong reductive {P 4 Mo 6 V } units, homo/hetero transition metal ions (Mn II /Co II Mn II ) and alkali metal ions (K + and/or Na + ). It is noted that the {P 4 Mo 6 V } cluster including the six Mo V atoms served as a multi-electron donor in the case of a photocatalytic reaction, while the transition metal ions functioned as catalytically active sites for adsorbing and activating CO 2 molecules. Additionally, the presence of alkali metal ions was believed to assist in the capture of more CO 2 for the photocatalytic reaction. The synergistic combination of the above-mentioned components in NENU-605 and NENU-606 effectively facilitates the accomplishment of the required eight-electron transfer process for CH 4 evolution. Furthermore, NENU-606 containing hetero-metallic active sites finally exhibited higher CH 4 generation selectivity (85.5%) than NENU-605 (76.6%).

Metal-organic frameworks (MOFs) with high porosity could act as an ideal substitute for supercapacitors, but their poor electrical conductivities limit their electrochemical performances. In order to overcome this problem, conductive polypyrrole (PPy) has been introduced and a novel nanocomposite resulting from polyoxometalate (POM)-based MOFs (NENU-5) and PPy has been reported. It comprises the merits of POMs, MOFs, and PPy. Finally, the highly conductive PPy covering the surfaces of NENU-5 nanocrystallines can effectively improve the electron/ion transfer among NENU-5 nanocrystallines. The optimized NENU-5/PPy nanocomposite (the volume of Py is 0.15 mL) exhibits high specific capacitance (5147 mF·cm -2 ), larger than that of pristine NENU-5 (432 mF·cm -2 ). Furthermore, a symmetric supercapacitor device based on a NENU-5/PPy-0.15 nanocomposite possesses an excellent areal capacitance of 1879 mF·cm -2 , which is far above other MOF-based supercapacitors.

Recently, development of a new type of anode material for lithium-ion batteries that possesses multielectron reaction, sufficient charge transfer, and restricted volume suppression has been considered a huge challenge. Herein, we find a simple hot-pressing method to incorporate polyoxometalate (POM)-based metal-organic frameworks (MOFs) onto three-dimensionally structured carbon cloth (CC), denoted as HP-NENU-5/CC, which immobilizes POMs into the MOFs avoiding the leaching of POMs and employs HP-NENU-5/CC as a flexible, conductive, and porous anode material. The HP-NENU-5/CC anode materials show outstanding electrochemical performance, exhibiting high reversible capacity (1723 mAh g -1 at 200 mA g -1 ), high rate capability (1072 mAh g -1 at 1000 mA g -1 ), and superior cycling stability (1072 mAh g -1 at 1000 mA g -1 after 400 cycles). Most importantly, the performance of HP-NENU-5/CC is the best among those of all reported POMs and MOF-based materials. In addition, we perform a comparative study for active materials coated on a two-dimensional current collector and CC, and our experimental results and analysis prove that the active material coated on CC does enhance the electrochemical performance.

Crystalline and porous covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H 2 evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH 2 -UiO-66 onto the surface of TpPa-1-COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H 2 evolution under visible light irradiation. Especially, NH 2 -UiO-66/TpPa-1-COF (4:6) exhibits the maximum photocatalytic H 2 evolution rate of 23.41 mmol g -1  h -1 (with the TOF of 402.36 h -1 ), which is approximately 20 times higher than that of the parent TpPa-1-COF and the best performance photocatalyst for H 2 evolution among various MOF- and COF-based photocatalysts., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite wide applications of bimetallic electrocatalysis in oxygen evolution reaction (OER) owing to their superior performance, the origin of the improved performance remains elusive. The underlying mechanism was explored by designing and synthesizing a series of stable metal-organic frameworks (MOFs: NNU-21-24) based on trinuclear metal carboxylate clusters and tridentate carboxylate ligands. Among the examined stable MOFs, NNU-23 exhibits the best OER performance; particularly, compared with monometallic MOFs, all the bimetallic MOFs display improved OER activity. DFT calculations and experimental results demonstrate that introduction of the second metal atom can improve the activity of the original atom. The proposed model of bimetallic electrocatalysts affecting their OER performance can facilitate design of efficient bimetallic catalysts for energy storage and conversion, and investigation of the related catalytic mechanisms., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Correction for 'A microporous Cu-MOF with optimized open metal sites and pore spaces for high gas storage and active chemical fixation of CO2' by Chao-Ying Gao et al., Chem. Commun., 2016, 52, 11147-11150.

Purpose: This study is a retrospective analysis evaluating the efficacy and toxicity of combination chemotherapy with Paclitaxel (PTX) and Oxaliplatin (OXA) as first-line treatment for patients with advanced gastric cancer (AGC)., Methods: One hundred and seven patients with locally advanced or metastatic gastric adenocarcinoma received intravenous infusions of PTX at 135 mg/m 2 and OXA at 85 mg/m 2 on day 1 every 14 days., Results: Among 107 patients enrolled, 9 patients could not be evaluated for a response because of the absence of any measurable lesions. Assessment of the response of 98 patients was made. The overall objective response rate was 42.9% (95% CI 32.9-52.8%), with two complete responses and 40 partial responses. The disease control was 79.6% (95% CI 71.5-87.7%). With 29 months of the median time of follow-up, the median progression-free survival was 5.8 months (95% CI 4.30-7.30 months) and the median overall survival was 11.5 months (95% CI 9.08-13.9 months). The 1-year survival rate was 48.0%. The most common grades 3 and 4 toxicities included neutropenia (32.7%), leucopenia (17.8%), fatigue (5.61%), and anemia (4.67%). Peripheral neuropathy occurred in 23.4% patients and grade 2 or higher peripheral neuropathy occurred in 12.1% of the patients., Conclusions: Combination chemotherapy with PTX and OXA offers a new, effective and safe regimen for patients with advanced gastric cancer.

Triazole, similarly to imidazole, makes a prominent contribution to the proton conductivity of porous materials. To investigate the effects of triazole-based ligands in polyoxovanadates (POVs) on proton conduction, we designed and synthesized two decavanadate-based POVs, [Zn 3 (C 2 H 4 N 4 ) 6 (H 2 O) 6 ](V 10 O 28 )·14H 2 O (1) and [Zn 3 (C 2 H 3 N 3 ) 8 (H 2 O) 4 ](V 10 O 28 )·8H 2 O (2) constructed from the ligands 3-amino-1,2,4-triazole and 1 H -1,2,4-triazole, respectively, via an aqueous solution evaporation method. Surprisingly, complex 1 obtained a superior proton conductivity of 1.24 × 10 -2 S cm -1 under 60 °C and 98% RH, which is much higher than that of complex 2. Furthermore, due to the contribution of the conjugate properties of the ligands to the third-order nonlinear optical (NLO) properties, we also studied its two-photon responses and achieved satisfactory results., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

With expanding human needs, many heavy metals were mined, smelted, processed, and manufactured for commercialization, which caused serious environmental pollutions. Currently, many adsorption materials are applied in the field of adsorption of heavy metals. Among them, the principle of many mercury adsorbents is based on the interaction between mercury and sulfur. Here, a S-containing metal-organic framework NENU-400 was synthesized for effective mercury extraction. Unfortunately, the skeleton of NENU-400 collapsed easily when exposed to the mercury liquid solution. To improve the stability, a synthetic strategy installing molecular building blocks (MBBs) into the channels was used. Modified by the MBBs, a more stable nanoporous framework was synthesized, which not only exhibits a high capacity of saturation mercury uptake but also shows high selectivity and efficient recyclability.

Molybdenum disulfide (MoS2)-based bimetallic sulfides have drawn increasing research attention because of their unique structures and properties. Herein, a one-pot hydrothermal synthesis method is proposed to grow a series of bimetallic sulfides on carbon cloth (M-Mo-S/CC, M = Co, Ni, Fe) using Anderson-type polyoxometalates (POMs) as bimetallic sources for the first time. An ideal model of M-Mo-S/CC was used to study the growth process through the nucleation-doping competition mechanism. It is proved for the first time that M-Mo-S/CC possess certain compositions of bimetallic sulfides rather than metal doped MoS2 structures because the nucleation reaction is predominant in the nucleation-doping competition. Moreover, the nucleation rates of different metals can be compared to study the different morphologies of M-Mo-S/CC because Anderson-type POMs have fixed bimetal proportions and precise structures. Co-Mo-S and Ni-Mo-S show spherical heterostructures with CoS2 or NiS mainly inside and interconnected MoS2 nanosheets outside, while Fe-Mo-S exhibits uniform nanosheet morphology without stacking. As electrodes for alkaline water electrolysis, M-Mo-S/CC with different compositions and morphologies exhibit a variety of activities. Particularly, among the M-Mo-S/CC samples, Co-Mo-S/CC achieves the best performance for hydrogen evolution reaction, oxygen evolution reaction and overall water splitting. This study presents a facile strategy of using POMs as bimetallic precursors for studying the growth mechanism as well as the water electrolysis performances of MoS2-based bimetallic sulfides.

We utilise the dual synthesis strategy in terms of bimetallic inorganic building blocks and sulfur containing organic ligand. A novel sulfur-containing bimetallic metal organic framework (Fe2Co-TPDC) with two types of 4-fold meso-helical structures has been successfully synthesized. Benefitting from the uniform distribution of active sulfur sites and the structural stability of the mixed-metallic method, Fe2Co-TPDC can efficiently prevent a shuttle behavior of sulfur and endow a commendable specific capacity. As far as we know, this is the first time that a sulfur-containing bimetallic crystalline MOF with helical structure and prominent specific capacity and remarkable cycling stability has served as an electrode material for LIBs.

For exploring the multifold helical fabrication of polyoxometalate (POM)-based hybrid compounds, four POM-based crystalline compounds with different meso-helices, H 3 [Ag 27 (trz) 16 (H 2 O) 6 ][SiW 12 O 40 ] 2 ·5H 2 O (1), H[Ag 27 (trz) 16 (H 2 O) 4 ][PW 12 O 40 ] 2 ·2H 2 O (2), [Ag 23 (trz) 14 (H 2 O) 2 ][HSiW 12 O 40 ] (3), and [Ag 23 (trz) 14 (H 2 O) 2 ][PW 12 O 40 ] (4), were successfully isolated by using the delicate 1,2,3-triazole ligand and silver ions in this work. Crystal analysis reveals that compounds 1 and 2 and compounds 3 and 4 are isomorphous and display 2-/4-fold mixed meso-helices and simple 2-fold meso-helices, respectively. In addition, due to the reversible multielectron redox behavior and electron storage functions of POMs, compounds 1 and 3 were studied as anode materials in lithium-ion batteries (LIBs). Compounds 1 and 3 show very high lithiation capacities (1356 and 1140 mAh g -1 , respectively) in the initial cycle, which are much higher than those of (NBu 4 ) 4 [SiW 12 O 40 ] and commercial graphite at the current density of 100 mA g -1 . More importantly, both compounds also show good stable performance after 100 cycles.

Three new proton conductors with simple structures based on isolated olyoxometalate anions as well as protonated imidazole and benzimidazole, namely, NNU-6-8, have been successfully prepared by hydrothermal reaction. We could control the number of proton sources by selecting different types and changing the charges of POM anions. The single crystal sample of NNU-6 along a-axis shows a highest proton conductivity of 1.91×10 -2  S cm -1 , which is two and three orders of magnitude higher than that of 2.42×10 -4 and 8.90×10 -5  S cm -1 along b- and c-axes, respectively, due to the more unobstructed H-bonding network and stronger π-π stacking between benzimidazole rings as proton-transferring pathway along a-axis than that along b and c axes. It is a straightforward model to understand the metaphysical proton-conducting process, and this is the first time to put forward the idea that π-π stacking could assist proton transfer and be in favor of proton conduction, which has been demonstrated by calculating potential energy surfaces of proton transfer between benzimidazole molecules., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Purpose: This study evaluated the efficacy and toxicity of combination chemotherapy with paclitaxel, oxaliplatin, 5-fluorouracil and leucovorin (POFL) in patients with recurrent or metastatic gastric cancer., Methods: One hundred and thirty-eight patients with histologically confirmed recurrent or metastatic gastric adenocarcinoma were treated with the POFL regimen: paclitaxel at a dose of 135 mg/m 2 as a 3-hour intravenous infusion on day 1, oxaliplatin 85 mg/m 2 and leucovorin 400 mg/m 2 as an intravenous infusion over 2 hours on day 1, followed by 5-fluorouracil 2,400 mg/m 2 as an infusion over a 46-hour period on 3 consecutive days, in a 2-week cycle., Results: Twelve patients could not be evaluated for response because of the absence of any measurable lesions or early discontinuation of therapy, so responses were assessed in 126 patients. The overall objective response rate was 56.3% (95% CI, 47.5%-64.9%). The median time to progression was 6.7 months (95% CI, 5.8-7.6 months), and the median overall survival was 12.6 months (95% CI, 11.3-13.9 months). The most common grade 3 and 4 toxicities were neutropenia (50.7%), peripheral neurotoxicity (16.7%) and alopecia (27.5%)., Conclusions: Combination chemotherapy with POFL offers a new, active and safe approach to the treatment of recurrent or metastatic gastric cancer.

Diabetic retinopathy (DR) is a major microvascular complication of diabetes, resulting in neuronal dysfunction, retinal vascular leakage, and apoptosis within the retina. Innate immunity plays an important role in the pathogenesis of type 2 diabetes (T2D) and related complications. The toll-like receptors (TLRs), central to innate immunity, are essential participants in the progression and pathogenesis of the disease and its complications. In the study, streptozotocin (STZ) was combined with whole-body hypoxia for quicker induction of early-stage diabetic retinopathy (DR) in the wild type (WT) and TLR7-knockout (KO) C57BL/6 mice. The effects of TLR7 were also investigated in fructose-treated retinal pigment epithelial (RPE) cells. In the retinas of WT/DR mice, abnormal a-wave and b-wave activity, hyperfluorescence, and reduced retinal thickness were observed. DR development was associated with enhanced TLR7 expression, whose deletion dramatically reduced VEGF expression levels. And the secretion of pro-inflammatory cytokines, such as tumor necrosis factor-α (TNF-α), interleukin (IL)-1β, IL-6, IL-18 and IL-12, was highly reduced by TLR7-deficiency in DR mice. Consistently, WT/DR mice exhibited higher phosphorylation of IκB kinase α (IKKα), inhibitor of NF-κB α (IκBα) and nuclear factor κB (NF-κB), which were found to be down-regulated in KO/DR mice. Similarly, DR-induced mitogen-activated protein kinases (MAPKs) activation was blocked by TLR7-knockout. In vitro, fructose incubation-triggered inflammation was reversed by TLR7 knockdown, accompanied with inactivated NF-κB and MAPKs pathways. And reduced reactive oxygen species (ROS) generation was observed in TLR7-knockdown cells with fructose treatment. Together, inhibiting TLR7 suppressed diabetic retinopathy by reducing inflammation and suggested a potential application in clinics., (Copyright © 2017. Published by Elsevier Inc.)

The difficulty of obtaining large single crystals of aluminum carboxylate metal-organic frameworks (MOFs) for structure determinations has limited the development of these water and thermally stable MOFs. Herein, how large single crystals of known MIL-53(Al) and the first two tetrahedral ligand-based, visible-light-absorbing 3D Al-MOFs, [Al 3 (OH) 3 (HTCS) 2 ] (AlTCS-1) and [Al 5 O 2 (OH) 3 (TCS) 2 (H 2 O) 2 ] (AlTCS-2; TCS=tetrakis(4-oxycarbonylphenyl)silane), are obtained in the presence of hydrofluoric or formic acid for conventional single-crystal diffraction measurements is presented. The technique of obtaining those single crystals has potential to be a general method for obtaining large and good-quality single crystals of Al-MOFs. AlTCS-1 and -2 are stable over a wide pH range (1-11), and AlTCS-1 is even stable in aqua regia solution for at least 24 h. The BET specific surface areas of AlTCS-1 and -2 are 11 and 1506 m 2  g -1 , respectively. AlTCS-2 takes up 51 cm 3  (STP) g -1 CO 2 and 15 cm 3  (STP) g -1 CH 4 at 298 K and 1 bar, which is relatively high among MOF materials. AlTCS-1 takes up 30 cm 3  g -1 CO 2 and 4.2 cm 3  g -1 CH 4 at 298 K and 1 bar. The rapid and stable photocurrent responses of AlTCS-1 and -2 under UV and visible-light illumination are observed. Moreover, AlTCS-1 photocatalyzes the water-splitting reaction under visible light with an average hydrogen evolution efficiency of 50 μmol g -1  h -1 for the first 10 h in a mixture of water and triethanolamine., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reported herein are two new polymorphic Co-MOFs (CTGU-5 and -6) that can be selectively crystallized into the pure 2D or 3D net using an anionic or neutral surfactant, respectively. Each polymorph contains a H 2 O molecule, but differs dramatically in its bonding to the framework, which in turn affects the crystal structure and electrocatalytic performance for hydrogen evolution reaction (HER). Both experimental and computational studies find that 2D CTGU-5 which has coordinates water and more open access to the cobalt site has higher electrocatalytic activity than CTGU-6 with the lattice water. The integration with co-catalysts, such as acetylene black (AB) leads to a composite material, AB&CTGU-5 (1:4) with very efficient HER catalytic properties among reported MOFs. It exhibits superior HER properties including a very positive onset potential of 18 mV, low Tafel slope of 45 mV dec -1 , higher exchange current density of 8.6×10 -4  A cm -2 , and long-term stability., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A nanocomposite polyoxomolybdate (PMo 12 )-polypyrrole (PPy)/reduced graphene oxide (RGO) is fabricated by using a simple one-pot hydrothermal method as an electrode material for lithium-ion batteries. This facile strategy skillfully ensures that individual polyoxometalate (POM) molecules are uniformly immobilized on the RGO surfaces because of the wrapping of polypyrrole (PPy), which avoids the desorption and dissolution of POMs during cycling. The unique architecture endows the PMo 12 -PPy/RGO with the lithium storage behavior of a hybrid battery-supercapacitor electrode: the nanocomposite with a lithium storage capacity delivers up to 1000 mAh g -1 at 100 mA g -1 after 50 cycles. Moreover, it still demonstrates an outstanding rate capability and a long cycle life (372.4 mAh g -1 at 2 A g -1 after 400 cycles). The reversible capacity of this nanocomposite has surpassed most pristine POMs and POMs-based electrode materials reported to date., Competing Interests: The authors declare no competing financial interest.

A novel polyoxometalate-based metal-organic framework (POMOF) with an ABW network, NENU-601, was synthesized in situ. To the best of our knowledge, this is the first POMOF with a zeolite-like structure, which was designed by regulating the length and angle of mixed ligands and rationally choosing suitable Polyoxometalates (POMs) as nodes.

Nanoporous Co-doped Zn 1-x Cd x S were facilely fabricated via adopting ZIFs as templates, and Cd(NO 3 ) 2 and thiourea as precursors. The highly porous microstructure and uniform Co-doping of the photocatalyst afford a high H 2 -production rate (45.2 and 422.2 times larger than those of Zn 0.5 Cd 0.5 S and CdS), providing an effective way for the development of high performance nanoporous photocatalysts.

A series of remarkable crystalline compounds containing metallapillararene/metallacalixarene metal-organic frameworks (MOFs), [Ag 5 (pyttz) 3 ·Cl·(H 2 O)][H 3 SiMo 12 O 40 ]·3H 2 O (1), [Ag 5 (trz) 6 ][H 5 SiMo 12 O 40 ] (2), [Ag 5 (trz) 6 ][H 5 GeMo 12 O 40 ] (3), and [Ag 5 (trz) 6 ][H 4 PW 12 O 40 ] (4) (pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, trz = 1,2,4-triazole), have been obtained by using a simple one-step hydrothermal reaction of silver nitrate, pyttz for 1 and trz for 2-4, and Keggin type polyoxometalates (POMs). Crystal analysis reveals that Keggin POMs have been successfully incorporated in the windows of the metallapillararene/metallacalixarene MOFs in compounds 1-4. In addition, the Keggin silicomolybdenate-based hybrid compounds 1 and 2 were used as anode materials in lithium ion batteries (LIBs), which exhibited promising electrochemical performance with the first discharge capacities of 1344 mAh g -1 for 1 and 1452 mAh g -1 for 2, and this stabilized at 520 mAh g -1 for 1 and 570 mAh g -1 for 2 after 100 cycles at a current density of 100 mA g -1 . The performances are better than that of (NBu 4 ) 4 [SiMo 12 O 40 ] matrix and commercial graphite anodes.

Two extremely rare β-cyclodextrin (β-CD) supported metal-organic frameworks (MOFs), CD-MOF-1 and CD-MOF-2, were induced to crystallize for the first time through a template-induced approach. The targeted CD-MOFs were employed to perform controlled drug delivery and cytotoxicity assays that confirmed their favourable biological potential of being used as drug carriers.