Tunable covalent benzo-heterocyclic rings constructed using two-dimensional conjugated polymers for visible-light-driven water splitting.

Developing highly efficient, stable, and cost-effective two-dimensional (2D) conjugated polymers (CPs) for overall water splitting (OWS) is critical for producing clean and renewable hydrogen energy, yet it remains a great challenge. Here, we designed eight 2D CPs through the topological assembly of diacetylene and benzene-derived molecular linkers that can offer active sites for hydrogen and oxygen evolution reactions, and explored their structural, electronic, optical, and photocatalytic OWS properties by performing first-principles computations. It is shown that incorporating benzo-heterocyclic rings into CPs can significantly modulate the electronic structures of CPs and broaden the spectral absorption, suitable for visible-light-driven OWS. Remarkably, through a range of screening criteria, including stability, electronic band structures, band edge alignments, and photocatalytic activity, we found that CP-4 based on diacetylene and benzotrifuran can spontaneously trigger the OWS in a neutral environment under its own light-induced bias, eliminating the need for sacrificial agents or cocatalysts. Specifically, the HER active site is primarily located at diacetylene moieties, while the OER active site is mainly concentrated on the benzo-heterocyclic rings. Moreover, the ideal STH efficiency for OWS on CP-4 was estimated to be 13.87%, highlighting its potential as a prospective photocatalyst for large-scale industrial OWS. Our findings open a door to the rational design of novel polymer photocatalysts for OWS.

Predictors of successful endovascular recanalization in patients with symptomatic nonacute intracranial large artery occlusion.

BACKGROUND: Endovascular recanalization in patients with symptomatic nonacute intracranial large artery occlusion (ILAO) has been reported to be feasible, but technically challenging. This study aimed to determine the predictors of successful endovascular recanalization in patients with symptomatic nonacute ILAO. METHODS: The outcomes of endovascular recanalization attempts performed in 70 consecutive patients showing symptomatic nonacute ILAO with hemodynamic cerebral ischemia between January 2016 to December 2022 were reviewed. Potential variables, including clinical and radiological characteristics related to technical success, were collected. Univariate analysis and multivariate logistic regression were performed to identify predictors of successful recanalization for nonacute ILAO. RESULTS: Technically successful recanalization was achieved in 57 patients (81.4%). The periprocedural complication rate was 21.4% (15 of 70), and the overall 30-day morbidity and mortality rates were 7.1% (5 of 70) and 2.9% (2 of 70), respectively. Univariate analysis showed that successful recanalization was associated with occlusion duration, stump morphology, occlusion length, slow distal antegrade flow sign, and the presence of bridging collateral vessels. Multivariate analysis showed that occlusion duration ≤ 3 months (odds ratio [OR]: 22.529; 95% confidence interval [CI]: 1.636-310.141), tapered stump (OR: 7.498; 95% CI: 1.533-36.671), and occlusion length < 10 mm (OR: 7.049; 95% CI: 1.402-35.441) were independent predictive factors for technical success of recanalization. CONCLUSIONS: Occlusion duration ≤ 3 months, tapered stump, and occlusion length < 10 mm were independent positive predictors of technical success of endovascular recanalization for symptomatic nonacute ILAO. These findings may help predict the likelihood of successful recanalization in patients with symptomatic nonacute ILAO and also provide a reference for the selection of appropriate patients. Further prospective and multicenter studies are required to validate our findings.

Efficient Electrochemical Detection of Hydrogen Peroxide Based on Silver-Centered Preyssler-Type Polyoxometalate Hybrids.

Four polyoxometalate (POM)-based organic-inorganic hybrid compounds, namely, (H2bimb)6H8[((Mn(H2O)3(µ-bimb))0.5(Mn(H2O)4)(Mn(H2O)5)0.5(AgP5W30O110))2]·29H2O (1), [(Cu(Hbimb)(H2O)2(µ-bimb)Cu(Hbimb)(H2O))(Cu(H2O)2(µ-bimb)Cu(H2O)3)((Cu(H2O)2)0.5(µ-bimb)(Cu(H2O)3)0.5)H2(AgP5W30O110)]·12.5H2O (2), (H2bimb)2H[(Zn(Hbimb)(H2O)4(Zn(Hbimb)(H2O)2)0.5)2(AgP5W30O110)]·12H2O (3), and (H2bimb)3H2[(Ag(H2O)2)0.5(Ag(Hbimb)Ag(Hbimb)(µ-bimb)Ag)(Ag(H2O)2)0.5(AgP5W30O110)]·7H2O (4) (bimb = 1,4-bis(1H-imidazol-1-yl)benzene), were hydrothermally synthesized using a silver-centered Preyssler-type POM K14[AgP5W30O110]·18H2O (abbreviated as K-{AgP5W30}) as a precursor. In 1-4, {AgP5W30} clusters integrating the merits of Ag+ and {P5W30} units are modified by different transition metal (TM)-organic fragments to extend the structures into three-dimensional frameworks. As nonenzymatic electrochemical sensor materials, 1-4 show good electrocatalytic activity, high sensitivity, and a low detection limit for detecting hydrogen peroxide (H2O2); 4 possesses the highest sensitivity of 195.47 µA·mM-1·cm-2 for H2O2 detection. Most importantly, the average level of H2O2 detection of these {AgP5W30}-based materials outperforms that of Na-centered Preyssler-type {NaP5W30} and most Keggin-type POM-based materials. The performances of such {AgP5W30} materials mainly stem from the unique advantage of high-negatively charged {AgP5W30} clusters together with the good synergistic effect between {AgP5W30} and TMs. This work expands on the research of high-efficiency POM-based nonenzymatic electrochemical H2O2 sensors using Ag-containing POMs with high negative charges, which is also of great theoretical and practical significance to carry out health monitoring and environmental analysis.

Two-dimensional ultrathin surfactant-encapsulating polyoxometalate assemblies as carriers for monodispersing noble-metal nanoparticles with high catalytic activity and stability.

Noble metal nanoparticles (NMNPs) with excellent catalytic activity and stability play an important role in the field of environmental governance. A uniform distribution and a strong binding force with the carriers of the noble metal nanoparticles are important, but avoidance of the use of additional reducing agents is a promising direction of research. Herein, 2D ultrathin surfactant-encapsulating polyoxometalate (SEP) nanosheets constructed by the self-assembly of dodecyldimethylammonium bromide (DODA) and molybdophosphate (H3PMo12O40, PMo12) are designed to be versatile carriers for Ag nanoparticles. Under the synergistic effect of the well-arranged PMo12 units, encapsulating hydrophobic oleic acid (OA) and reductive molybdophosphate under Xe lamp irradiation, the silver oleate (AgOA)-derived Ag nanoparticles (5 ± 2 nm) are monodispersed on the DODA-PMo12 assemblies and form the Agx/DODA-PMo12 composite. The optimized Ag4.89/DODA-PMo12 composite exhibits high catalytic activity and stability in the degradation of 4-nitrophenol (4-NP), which reaches a superior rate constant of 6.49 × 10-3 s-1 and without significant deterioration after three recycles. This technique can be facilely promoted to other noble metal nanoparticles with excellent catalytic activity and stability.

Endovascular Treatment of Complex Vascular Diseases of the Internal Carotid Artery Using the Willis Covered Stent: Preliminary Experience and Technical Considerations.

Purpose: The Willis covered stent (WCS) is used to treat complex vascular diseases of the internal carotid artery; however, its performance requires further investigation. This study aimed to present our single-center clinical results and experience of endovascular repair of complex vascular diseases of the internal carotid artery using the WCS. Methods: Patients who presented with complex vascular diseases of the internal carotid artery and who were treated with the WCS from December 2013 to September 2018 were retrospectively reviewed. Procedural results, perioperative complications, incidence of endoleak, and follow-up outcomes were analyzed. Results: Sixty-five patients were enrolled. A total of 25 large aneurysms, 10 pseudoaneurysms, 14 blood blister-like aneurysms, 11 carotid-cavernous fistulas, and 5 surgical injuries were assessed. WCS placement was successful in all patients. Immediate angiography showed that complete repair of the target artery was achieved in 56 patients (86.2%). Endoleak was observed in nine patients, including seven type I endoleaks and two type II endoleaks. Occlusion of a side-branch vessel occurred in four patients. Acute in-stent thrombosis occurred in one patient. No ischemic or hemorrhagic events or other complications developed during the perioperative and follow-up periods. Angiographic follow-up (mean duration, 12 ± 3.29 months) was performed in 60 patients and showed complete target artery repair in 58 patients, and asymptomatic mild to moderate in-stent stenosis was observed in four patients. Slight endoleak persisted in two patients without enlargement or rupture of the residual lumen. Conclusion: WCS implantation is safe, feasible, and efficacious for endovascular repair in patients with complex vascular diseases of the internal carotid artery, showing excellent short-term target artery patency and clinical outcomes.

Construction of the 1D Covalent Organic Framework/2D g-C3N4 Heterojunction with High Apparent Quantum Efficiency at 500 nm.

The reasonable construction of heterojunction photocatalysts with clear nanostructures and a good interface contact especially the one-dimensional/two-dimensional (1D/2D) composite heterojunction with unique morphology is considered one of the most effective strategies for designing highly efficient photocatalysts. Herein, a series of the 1D ß-keto-enamine-based covalent organic framework (COF)/2D g-C3N4 composite materials COF-CN (1:x; where 1:x represents the mass ratio of COF and g-C3N4, x = 2.5, 5, 10, 15, 20) is prepared through the in situ reaction of 2,4,6-triformylphloroglucinol (Tp) and benzidine (BD) in stripped g-C3N4 suspension. A series of characterizations, such as X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), have verified their 1D/2D heterojunction structure. With the introduction of 1D COF nanobelts, the absorption of the composite is largely extended to 560 nm. Photocatalytic experiments reveal that the composite COF/CN shows evidently superior photocatalytic performance than individual COF and g-C3N4. The optimized COF-CN (1:10) exhibits a H2 production rate of 12.8 mmol g-1·h-1 under visible-light (λ ≥ 420 nm) irradiation, which is about 62 and 284 times higher than those of COF and g-C3N4, respectively. The apparent quantum efficiency (AQE) of COF-CN (1:10) is about 15.09% under 500 nm light irradiation, which is one of the highest among previous COF- or g-C3N4-based materials. This work provides important strategies for designing and constructing high-efficiency heterojunction photocatalysts with multidimensional features.

Pt-O bond as an active site superior to Pt0 in hydrogen evolution reaction.

The oxidized platinum (Pt) can exhibit better electrocatalytic activity than metallic Pt0 in the hydrogen evolution reaction (HER), which has aroused great interest in exploring the role of oxygen in Pt-based catalysts. Herein, we select two structurally well-defined polyoxometalates Na5[H3Pt(IV)W6O24] (PtW6O24) and Na3K5[Pt(II)2(W5O18)2] (Pt2(W5O18)2) as the platinum oxide model to investigate the HER performance. Electrocatalytic experiments show the mass activities of PtW6O24/C and Pt2(W5O18)2/C are 20.175 A mg-1 and 10.976 A mg-1 at 77 mV, respectively, which are better than that of commercial 20% Pt/C (0.398 A mg-1). The in situ synchrotron radiation experiments and DFT calculations suggest that the elongated Pt-O bond acts as the active site during the HER process, which can accelerate the coupling of proton and electron and the rapid release of H2. This work complements the knowledge boundary of Pt-based electrocatalytic HER, and suggests another way to update the state-of-the-art electrocatalyst.

Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction.

The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) involves a variety of electron transfer pathways, resulting in poor reaction selectivity, limiting its use to meet future energy requirements. Polyoxometalates (POMs) can both store and release multiple electrons in the electrochemical process, and this is expected to be an ideal "electron switch" to match with catalytically active species, realize electron transfer modulation and promote the activity and selectivity of the electrocatalytic CO2RR. Herein, we report a series of new POM-based manganese-carbonyl (MnL) composite CO2 reduction electrocatalysts, whereby SiW12-MnL exhibits the most remarkable activity and selectivity for CO2RR to CO, resulting in an increase in the faradaic efficiency (FE) from 65% (MnL) to a record-value of 95% in aqueous electrolyte. A series of control electrochemical experiments, photoluminescence spectroscopy (PL), transient photovoltage (TPV) experiments, and density functional theory (DFT) calculations revealed that POMs act as electronic regulators to control the electron transfer process from POM to MnL units during the electrochemical reaction, enhancing the selectivity of the CO2RR to CO and depressing the competitive hydrogen evolution reaction (HER). This work demonstrates the significance of electron transfer modulation in the CO2RR and suggests a new idea for the design of efficient electrocatalysts towards CO2RR.

Reduced State of the Graphene Oxide@Polyoxometalate Nanocatalyst Achieving High-Efficiency Nitrogen Fixation under Light Driving Conditions.

The nitrogen (N2) reduction to generate ammonia (NH3) is a prerequisite for inputting fixed nitrogen (N) into a global biogeochemical cycle. Developing highly efficient photocatalysts for N2 fixation under mild conditions is still a challenge. Herein, we first report three kinds of reduction states of graphene oxide (GO)@polyoxometalate (POM) composite nanomaterials, which have outstanding photocatalytic N2 fixation activities in pure water without any other electronic sacrificial agents and cocatalysts at atmospheric pressure and room temperature. A lot of experiments show that the remarkable photocatalytic N2 fixation performance of these three nanocatalysts is due to three factors that doping the reduced POMs (also called heteropoly blues) into the reduce GO (rGO) reduces the aggregation state of rGO (from 5 to 2 nm), resulting in rGO exposing many active sites to enhance the N2 adsorption amount, these three nanocatalysts possess a wide absorption spectrum and strong reducibility, which facilitate absorb light energy exciting abundant photoelectrons to activate N2, and rGO can effectively suppress the electrons recombination and rapidly transfer electrons to the absorbed N2 to accelerate NH3 production. Among them, r-GO@H5[PMo10V2O40] (PMo10V2) exhibits the highest NH3 generation efficiency of 130.3 µmol L-1 h-1, which is improved by 65.9 and 97.3% compared to the reduced PMo10V2 (rPMo10V2) and PMo10V2. Introduction of POMs provides a new perspective in the design of high-performance photocatalytic N2 fixation nanomaterials.

Two-dimensional polyimide heterojunctions for the efficient removal of environmental pollutants under visible-light irradiation.

Two-dimensional (2D) heteromaterials with large interface contact and intimate interfacial charge transition have been considered to be an ideal model for constructing highly efficient photocatalysts. However, few studies have reported on these 2D heterojunctions. Herein, we report a series of new 2D heterojunctions comprising polyimide (PI) and perylene-3,4,9,10-tetracarboxylic dianhydride (TD). These heterojunctions, denoted as PI-TDx (where x represents the amount of TD added, i.e., x = 0.13, 0.18, 0.27, 0.54, and 1.08 g), were prepared by the solid thermal copolymerization of melamine (MA), pyromellitic dianhydride (PD), and different amounts of TD. FT-IR spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy analyses were used to verify the 2D heterojunction structure. Photocatalytic experiments reveal that PI-TDx exhibit excellent and stable photocatalytic performance for the degradation of the organic dyes rhodamine B (RhB) and methyl violet (MV), as well as for the photoreduction of Cr(vi), under visible-light irradiation. Among the samples, PI-TD0.18 exhibits the best photocatalytic performance. Its activity is about 2.7 times and 7.5 times higher than that of individual PIMP (formed by MA and PD) and PIMT (formed by MA and TD) for RhB degradation, respectively. Notably, PI-TD0.18 retains a certain photocatalytic activity under light irradiation at 600 nm. The photocatalytic-mechanism study demonstrates that PI-TD0.18 has a classic type-II heterojunction. Its 2D heterojunction greatly enhances the visible-light absorption of the composites and effectively suppresses the radiation recombination of photogenerated carriers, thereby improving its charge transfer and separation abilities and providing excellent photocatalytic performance. This work may serve as an important reference for the design and construction of new highly efficient 2D organic conjugated-polymer photocatalysts.

Endovascular recanalization for symptomatic subacute and chronic intracranial large artery occlusion of the anterior circulation: initial experience and technical considerations.

PURPOSE: This study aimed to report the clinical findings and initial clinical experience of endovascular recanalization for symptomatic subacute/chronic intracranial large artery occlusion (ILAO) of the anterior circulation. METHODS: From October 2015 to December 2017, 13 patients with symptomatic subacute/chronic ILAO of the anterior circulation were enrolled in this study and underwent endovascular recanalization. We collected the initial procedural results, including the rate of successful recanalization and periprocedural complications, and data pertaining to angiographic and clinical follow-up. RESULTS: Recanalization was successful in 11 of 13 patients (84.6%). Intraoperative complications occurred in four cases, including symptomatic distal embolism in three cases; one of which was simultaneously complicated with artery dissection. Intracerebral hemorrhage occurred in one case. Eleven patients underwent angiographic follow-up, and 12 patients underwent clinical follow-up. The results of the angiography follow-up (mean 6 ± 3.29 months) showed that in-stent restenosis occurred in one of the 11 successfully recanalized patients. However, the artery was occluded again in the patient who achieved thrombolysis in cerebral infarction (TICI) grade of 2a after treatment. Clinical follow-up (mean 5.8 ± 2.25 months) showed no recurrence of transient ischemic attack (TIA) or stroke in ten successfully recanalized cases. However, the patient who developed in-stent stenosis suffered TIA. CONCLUSIONS: Endovascular recanalization for symptomatic subacute/chronic ILAO of anterior circulation is feasible, relatively safe, and efficacious in highly selected cases, improving patients' symptoms in the short-term. However, further larger scale pilot studies are needed to determine the efficacy and long-term outcome associated with this treatment.

A single-center experience in the endovascular treatment of carotid siphon aneurysms using the Willis covered stent: a retrospective analysis.

OBJECTIVE: To report the clinical results and initial clinical experience of endovascular isolation with the Willis covered stent for carotid siphon aneurysms. METHODS: Between November 2013 and December 2016, a total of 57 patients who presented with carotid siphon aneurysms were treated with the Willis covered stent. Results of the procedures, technical events, and complications were recorded. Clinical and imaging follow-ups were performed at 3 months following the endovascular procedures. RESULTS: Placement of the Willis covered stent was successful in all patients. Immediate angiography revealed complete exclusion of aneurysms in 48 patients (84%), while endoleak occurred in nine patients (16%). Procedure-related complications occurred in three cases, including displacement of the covered stent in one patient, acute in-stent thrombosis in one patient, and microwire-related intracranial hemorrhage in one patient. Angiographic follow-ups were done in 49 patients, with complete exclusion of aneurysms in 47 patients. Endoleak was present in two patients. No aneurysm recurrence occurred. Forty-four patients showed good parent artery patency, while the other five patients showed mild to moderate asymptomatic in-stent stenosis. During the follow-up period, no ischemic or hemorrhagic event occurred. The modified Rankin Scale scores at follow-up were 0-2 in 56 patients and >2 in one patient. CONCLUSIONS: The treatment of siphon aneurysms with Willis covered stent implantation resulted in satisfactory clinical outcomes. The Willis covered stent seems safe and feasible for the treatment of siphon aneurysms, which still needs to be confirmed by longer follow-up periods and controlled studies with larger samples.

MoP/Mo2C@C: A New Combination of Electrocatalysts for Highly Efficient Hydrogen Evolution over the Entire pH Range.

During the exploration of highly efficient noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER), a promising and challenging strategy is to fabricate composite nanocatalysts by finely tuning metal and/or nonmetal element components. Herein, we report a new HER electrocatalyst, which is composed of molybdenum phosphide and molybdenum carbide composite nanoparticles (NPs) coated by few-layer N-doped graphitic carbon shells (denoted as MoP/Mo2C@C). Such a new combination mode of electrocatalysts is realized by a one-step annealing route with the mixture of a Mo/P-based polyoxometalate (POM) and dicyandiamide. On the basis of this method, the simultaneous phosphorization and carbonization in a nanoscale confined space can be easily achieved by the use of POM as the molecular-element-regulating platform. MoP/Mo2C@C exhibits more remarkable HER performance over the whole pH range than those of MoP, Mo2C, and the physical mixture of MoP and Mo2C. The low overpotentials of 89, 136, and 75 mV were obtained at a current density of 10 mA cm-2 in the media of pH = 0, 7, and 14, respectively. Furthermore, MoP/Mo2C@C shows a long-term durability for 14 h over the entire pH range (0-14). Because of the protection of carbon shells, such composite electrocatalyst also possesses better transition-metal tolerance exemplified by Fe2+, Co2+, and Ni2+ than that of 20% commercial Pt/C. This work demonstrates the advantage of POM precursors in adjusting the component and properties of nanoscale composite electrocatalysts for HER, which may suggest new options for the fabrication of highly efficient composite electrocatalysts.

Ag/AgxH3-xPMo12O40 Nanowires with Enhanced Visible-Light-Driven Photocatalytic Performance.

Photocatalysis, a promising technology platform to address the environmental problems, has been attracting considerable attention. In this paper, Ag/AgxH3-xPMo12O40 (simplified as Ag/AgHPMo12) nanowires have been synthesized by a facile solid reaction route and in situ photodeposited method. The results of SEM and TEM indicate that the diameters of AgHPMo12 nanowires are about 45 ± 10 nm, and Ag nanoparticles with diameters in the range of 5-15 nm are uniformly anchored on the surface of AgHPMo12 nanowires. The Ag content in the Ag/AgHPMo12 composite was manipulated by the light irradiation time (Ag/AgHPMo12-x; x stands for the irradiation time; x = 2, 4, 6, 8 h, respectively). With increasing irradiation time, the light absorption of as-synthesized samples in the visible region was gradually enhanced. The Ag/AgHPMo12-4 exhibits the best photocatalytic performance for the degradation of methyl orange and reduction of Cr2O72- under visible-light (λ > 420 nm) irradiation. The study of the photocatalytic mechanism reveals that both Ag and AgHPMo12 can be excited by visible light. The photoinduced electrons were transferred from AgHPMo12 to metallic Ag, and combined with the Ag plasmonic holes. The Ag plasmonic electrons were trapped by O2 to form ·O2-, or directly reduced Cr2O72- to Cr3+. Meanwhile, the ·O2- species and the photogenerated holes of AgHPMo12 were used to oxidize MO or i-PrOH; thus, they showed highly efficient and recyclable photocatalytic performance for removing the organic and inorganic pollutants.

Endovascular isolation of intracranial blood blister-like aneurysms with Willis covered stent.

OBJECTIVE: Intracranial blood blister-like aneurysm (BBA) is a rare type of aneurysm that lacks all layers of the arterial wall. These fragile aneurysms have the propensity to rupture with minimal manipulation, which makes them hazardous and difficult to treat. The present study evaluated the safety and feasibility of endovascular treatment of BBAs with the Willis covered stent. MATERIALS: Thirteen patients (7 men and 6 women, age range 28-68 years) who presented with ruptured BBAs and were treated with the Willis covered stent were retrospectively reviewed. Results of the procedures and treatment-related complications were recorded. Angiographic and clinical follow-ups were performed 4-6 months after the procedure. RESULTS: Placement of the covered stent was successful in all patients. Immediate angiography showed complete aneurysm occlusion in 12 patients while one patient showed a mild endoleak. This high rate of aneurysm exclusion ensured the security of postoperative antiplatelet treatment. Occlusion of the ophthalmic artery occurred in two patients and occlusion of the anterior choroidal artery occurred in one patient; however, none of them showed acute or delayed clinical symptoms. Thrombosis, aneurysm rupture, and other complications did not develop in any case. Angiographic follow-up showed complete aneurysm exclusion without aneurysm recurrence in any patients. Only two patients showed asymptomatic mild to moderate in-stent stenosis. All patients had satisfactory clinical outcomes (modified Rankin Scale score ≤1). CONCLUSIONS: Willis covered stent implementation may be safe and feasible for BBAs. This strategy might be a promising option for this high-risk type of aneurysm.

A Surfactant-Encapsulating Polyoxometalate Nanowire Assembly as a New Carrier for Nanoscale Noble-Metal Catalysts.

The loading of noble-metal nanoparticles (NMNPs) onto various carriers to obtain stable and highly efficient catalysts is currently an important strategy in the development of noble metal (NM)-based catalytic reactions and their applications. We herein report a nanowire supramolecular assembly constructed from the surfactant-encapsulating polyoxometalates (SEPs) CTAB-PW12 , which can act as new carriers for NMNPs. In this case, the Ag NPs are loaded onto the SEP nanowire assembly with a narrow size distribution from 5 to 20 nm in diameter; the average size is approximately 10 nm. The Ag NPs on the nanowire assemblies are well stabilized and the over agglomeration of Ag NPs is avoided owing to the existence of well-arranged polyoxometalate (POM) units in the SEP assembly and the hydrophobic surfactant on the surface of the nanowire assembly. Furthermore, the loading amount of the Ag NPs can be adjusted by controlling the concentration of the AgNO3 aqueous solution. The resultant Ag/CTAB-PW12 composite materials exhibit high activity and good stability for the catalytic reduction of 4-nitrophenol (4-NP) with NaBH4 in isopropanol/H2 O solution. The NMNPs-loaded SEP nanoassembly may represent a new composite catalyst system for application in NM-based catalysis.

Highly Dispersed Polyoxometalate-Doped Porous Co3 O4 Water Oxidation Photocatalysts Derived from POM@MOF Crystalline Materials.

Rational design of earth-abundant photocatalysts is an important issue for solar energy conversion and storage. Polyoxometalate (POM)@Co3 O4 composites doped with highly dispersive molecular metal-oxo clusters, synthesized by loading a single Keggin-type POM cluster into each confined space of a metal-organic framework (MOF), exhibit significantly improved photocatalytic activity in water oxidation compared to the pure MOF-derived nanostructure. The systematic synthesis of these composite nanocrystals allows the conditions to be tuned, and their respective water oxidation catalytic performance can be efficiently adjusted by varying the thermal treatment temperature and the feeding amount of the POM. This work not only provides a modular and tunable synthetic strategy for preparing molecular cluster@TM oxide (TM=transition metal) nanostructures, but also showcases a universal strategy that is applicable to design and construct multifunctional nanoporous metal oxide composite materials.

Black-colored ZnO nanowires with enhanced photocatalytic hydrogen evolution.

Black-colored ZnO nanowires have been prepared in a metal-organic chemical vapor deposition system by employing a relatively low growth temperature and oxygen-deficient conditions. X-ray photoelectron spectroscopy reveals the incorporation of carbon into the nanowires. The photocatalytic hydrogen evolution activity of the black-colored ZnO nanowires is over 2.5 times larger than that of the pristine ZnO nanowires under simulated solar illumination conditions, and the enhanced photocatalytic activity can be attributed to the higher absorption of visible light by the black color and better carrier separation at the ZnO/carbon interface.

Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction.

Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials.

Hybrid Coordination Networks Constructed from ɛ-Keggin-Type Polyoxometalates and Rigid Imidazole-Based Bridging Ligands as New Carriers for Noble-Metal Catalysts.

Three hybrid coordination networks that were constructed from ɛ-Keggin polyoxometalate building units and imidazole-based bridging ligands were prepared under hydrothermal conditions, that is, H[(Hbimb)2 (bimb){Zn4 PMo(V8) Mo(VI) 4O40}]⋅6 H2O(1), [Zn(Hbimbp)(bimbp)3 {Zn4 PMo(V8) Mo(VI) 4O40}]⋅DMF⋅3.5 H2O(2), and H[Zn2 (timb)2 (bimba)2 Cl2 {Zn4 PMo(V8) Mo(VI) 4O40}]⋅7 H2O(3) (bimb=1,4-bis(1-imidazolyl)benzene, bimbp=4,4'-bis(imidazolyl)biphenyl, timb=1,3,5-tris(1-imidazolyl)benzene, bimba=3,5-bis(1-imidazolyl)benzenamine). All three compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The mixed valence of the Mo centers was analyzed by XPS spectroscopy and bond-valence sum calculations. In all three compounds, the ɛ-Keggin polyoxometalate (POM) units acted as nodes that were connected by rigid imidazole-based bridging ligands to form hybrid coordination networks. In compound 1, 1D zigzag chains extended to form a 3D supramolecular architecture through intermolecular hydrogen-bonding interactions. Compound 2 consisted of 2D curved sheets, whilst compound 3 contained chiral 2D networks. Because of the intrinsic reducing properties of ɛ-Keggin POM species, noble-metal nanoparticles were loaded onto these POM-based coordination networks. Thus, compounds 1-3 were successfully loaded with Ag nanoparticles, and the corresponding composite materials exhibited high catalytic activities for the reduction of 4-nitrophenol.