Self-Reconstructed Two-Dimensional Cluster-Based Co-Organic Layer Heterojunctions for Enhanced Oxygen Evolution Reactions.

When it comes to an efficient catalytic oxygen evolution reaction (OER) in the production of renewable energy and chemicals, the construction of heterogeneous structures is crucial to break the linear scalar relationship of a single catalyst. This heterogeneous structure construction helps creatively achieve high activity and stability. However, the synthesis process of heterogeneous crystalline materials is often complex and challenging to capture and reproduce, which limits their application. Here, the dynamic process of structural changes in Co-MOFs in alkali was captured by in situ powder X-ray diffraction, FT-IR spectroscopy, and Raman spectroscopy, and several self-reconfigured MOF heterogeneous materials with different structures were stably isolated. The created ß-Co(OH)2/Co-MOF heterojunction structure facilitates rapid mass-charge transfer and exposure of active sites, which significantly enhanced OER activity. Experimental results show that this heterogeneous structure achieves a low overpotential of 333 mV at 10 mA cm-2. The findings provide new insights and directions for the search for highly reactive cobalt-based MOFs for sustainable energy technologies.

Graphene oxide enabled self-assembly of silver trimolybdate nanowires into robust membranes for nanosolid capture and molecular separation.

A graphene oxide (GO) assisted self-assembly strategy for growing a silver trimolybdate nanowire membrane with capabilities of nanosolid capture and small molecule separation is reported. Thanks to the GO bridges and the accurate self-assembly process, the resulting membrane exhibits outstanding mechanical properties (can withstand 4300 times its weight) and impressively high porosity (97%). On the basis of the robustness and high porosity of the membrane, column-shaped filter apparatus has been fabricated, in which the membrane served as a self-standing permeation barrier to assess its permeability and practical application as a nanosolid filter and molecule filter. The permeability test of the membrane with pure water uncovers that the membrane exhibits fast permeability while driven by hydrostatic pressure only because of its significantly high porosity. The separation test of the membrane with P25 TiO2 solution, 13 nm Au solution, and yellow-emitting CdTe QDs reveals that all the tiny nanosolids are completely removed from the solution, which suggests that the membrane is an efficient nanosolid filter. Its efficiency is increased by the induction of surface collision from numerous nanowire barriers and the deposition of nanosolids on the nanowire surface. The separation test of the membrane with a mixed-dye solution reveals that sulfur containing methylene blue (MB) molecules are highly efficiently extracted under various chemical conditions, evidencing that the membrane is an ideal molecule filter too. Its high selectivity and high efficiency originated from the Ag-S bonding between the interlayered silver ions of the silver trimolybdate nanowire and the sulfur atom of MB molecules. Based on the above results, the silver trimolybdate nanowire membrane has been applied to purify drugs, which successfully removed sulbactam sodium impurity F from sulbactam sodium, demonstrating a purity increment from 98.92% to 99.93%. The present work should provide a significant step forward to bringing macroscopic 1D nanomaterial architectures much closer to real-world applications involving isolation and enrichment of catalyst reclamation, high-value chemical recovery, drug purification, and environmental remediation.

Removal of atrazine in catalytic degradation solutions by microalgae Chlorella sp. and evaluation of toxicity of degradation products via algal growth and photosynthetic activity.

Degradation solutions containing atrazine need to be further purified before they are discharged into the aquatic environment. With the objectives of evaluating removal capacity of the microalga Chlorella sp. toward atrazine in degradation solutions and toxicity of the degradation products, we investigated the removal efficiency (RE) and bioaccumulation of atrazine in the microalgae after an 8 d exposure to diluted degraded solutions containing 40 µg/L and 80 µg/L of atrazine as well as degradation products in the present study. Moreover, pure atrazine solutions with similar concentrations were simultaneously inoculated with the microalgae in order to distinguish the influence of the products. The photocatalytic degradation results showed that 31.4% of atrazine was degraded after 60 min, and three degradation products, desisopropyl-atrazine (DIA), desethyl-atrazine (DEA), and desethyl-desisopropyl-atrazine (DEIA) were detected. After an 8-d exposure, 83.0% and 64.3% of atrazine were removed from the degraded solutions containing 40 µg/L and 80 µg/L of atrazine, respectively. In comparison with the control, i.e., pure atrazine solution with equal concentration, Chlorella sp. in the degraded atrazine solution showed lower RE and growth rate. The photosynthetic parameters, especially performance index (PIABS), clearly displayed the differences between treatments. The values of PIABS of Chlorella sp. cultured in degradation atrazine for 8 days were significantly lower (P < 0.01) than that in the corresponding pure atrazine, suggesting potential inhibitory effect of degradation products on the microalgae. Atrazine and the degradation products inhibited algal photosynthesis via depressed light absorption and electron transport, and reduced utilization of light energy via energy dissipation. Our results demonstrated that microalgae Chlorella sp. had an encouraging atrazine removal potential and the degradation products of atrazine may inhibit algal growth and removal capability. This study may be useful for the application of microalgae in herbicide wastewater treatment and understanding algal removal of atrazine in natural aquatic environment.

Chemical-free fabrication of N, P dual-doped honeycomb-like carbon as an efficient electrocatalyst for oxygen reduction.

Heteroatom-doped nanoporous carbons are now emerging as alternatives to platinum and its alloys as electrocatalysts to facilitate oxygen reduction reaction in metal-air batteries and fuel cells. However, the synthesis of nanoporous carbons usually involve in complicated procedures and intensive chemicals, which may dramatically raise their manufacture cost that even surpasses that of precious platinum. Herein, we demonstrate the single-step, chemical-free fabrication of N, P dualdoped honeycomb carbon that has hierarchically porous structure and oxygen electrocatalysis activity close to the benchmark Pt/C. This material was fabricated through the direct pyrolysis of popcorn in a static, semi-opened environment. With this strategy, nitrous and phosphoric groups from proteins and phosphates within the popcorn are condensed with graphitic matrix to form NC and PC bonds, and pyrolysis byproducts (such as H2O and CO2) can etch disordered carbon domains to form hierarchical pores and edge carbons. Practical test of this honeycomb carbon as air electrode of a primary Zn-air battery shows an open-circuit potential of 1.44V and peak power density of 36.6mWcm-2 that is even better than Pt/C. The impact of this work is that it will facilitate the targeted design and cost-saved fabrication of metal-free catalysts for electrocatalytic applications.

BiOBr nanoplates@TiO2 nanowires/carbon fiber cloth as a functional water transport network for continuous flow water purification.

A novel BiOBr@TiO2/carbon hybrid framework as a continuous flow sunlight water purification system has been reported in the present work. The BiOBr@TiO2/carbon hybrid framework was fabricated via the sequential growth of TiO2 nanowires and BiOBr nanoplates on carbon fiber cloth. TiO2 nanowires interweaved with carbon fibers to form a porous network, while BiOBr nanoplates were arrayed on TiO2 nanowires. The obtained BiOBr@TiO2/carbon hybrid framework possesses numerous micro/nanochannels between their adjacent one-dimensional building blocks, which can serve as an effective water transport network driven by capillary force. Furthermore, BiOBr@TiO2/carbon hybrid frameworks exhibit impressive sunlight-driven photocatalytic activity and adsorption ability because of their enhanced sunlight absorption ability, efficient charge separation features, and mesoporous architecture. The excellent reusability and durability of the BiOBr@TiO2/carbon hybrid frameworks have also been confirmed. A novel BiOBr@TiO2/carbon hybrid framework based continuous flow sunlight water purification system with a high water purification efficiency (305.6 L h-1 m-2) has been constructed in the present work. All the features make the BiOBr@TiO2/carbon hybrid framework a promising material suitable for water purification.

Adsorption characteristics of bio-adsorbent on chromium(III) in industrial wastewater.

The removal of chromium(III) (Cr(III)) from industrial wastewater by various low-cost methods has been widely investigated. In this paper, a type of bio-adsorbent was prepared using rice straw modified by fermentation and simple chemical treatment. The aim is to detect the adsorption mechanism and characteristics on Cr(III) ions. The analysis shows that the bio-adsorbent possesses four modified characteristics for Cr(III) adsorption. The first one is the acquired physical adsorption involving concave and convex structures. The second one is the effects of the hydrogen bonding surface hydroxyl groups and the metal chromium ion with complexation. The third one is mainly caused by hydrophilic active groups that possess carboxyl and hydroxyl groups during microbial degradation to combine with ions. The final one is the bio-adsorbent had high adsorption for low concentration of Cr(III) ions. The highest removal of around 97.45% was obtained at pH 5.0, bio-adsorption dosage of 0.5 g L(-1), and initial Cr(III) concentration of 20 mg L(-1). The adsorption process followed the pseudo second-order model (R(2) > 0.99), while the isotherms were fitted to the Freundlich equation (68.1926 mg g(-1)), mainly by chemical adsorption. This study demonstrates the potential of using this biosorbent to remove Cr(III) from both synthetic and industrial wastewater.

A new family of sunlight-driven bifunctional photocatalysts based on TiO2 nanoribbon frameworks and bismuth oxohalide nanoplates.

By taking advantage of the structural affinity between bismuth oxohalide and TiO2, we successfully prepare a family of hybrid frameworks via the designated growth of bismuth oxohalide nanoplates on TiO2 nanoribbons, and propose them as sunlight-driven bifunctional photocatalysts for all-weather removal of pollutants. The structural variability of bismuth oxohalide allows the optical absorption of the hybrid framework to be monotonically tuneable across the visible spectrum. Meanwhile, the hybridization greatly increases the surface roughness of the frameworks and enables the frameworks to harvest more photons to participate in photocatalytic reactions. Furthermore, the hybridization establishes two potential gradients to promote the separation of photo-induced electron-hole pairs: the internal electrical field perpendicular to the wide surfaces of bismuth oxohalide nanoplates and across the semiconductor-semiconductor heterojunction. Owing to the synergetic effects of the permeable mesoporous architecture, the intense visible light absorption, and the efficient charge separation, the hybrid frameworks are capable of all-weather removal of pollutants: they utilize the inter-ribbon pores to gather pollutants in the dark (behaving as collectors) and they rapidly degrade the pollutants in the day (behaving as photocatalysts). In particular, the BiOBr@TiO2 framework exhibits very impressive sunlight-driven photocatalytic activity, which is much higher than commercially available P25 TiO2 under the same conditions.

Self-assembled, robust titanate nanoribbon membranes for highly efficient nanosolid capture and molecule discrimination.

Supersaturation-directing self-assembly strategy for growing titanate nanoribbon membrane with capabilities of nanosolid capture and small molecule discrimination is reported. Owing to the distinct morphology of the nanoribbons and the accurate self-assembly process, the resulting membrane possesses outstanding mechanical properties (rupture strength exceeding 10 kg) and surprisingly high porosity (~97%), although there are no strong bonds among the nanoribbons. On the basis of the robustness of the membrane, we fabricated a column-shaped filter apparatus where the membrane acted as self-standing permeation barrier to evaluate its permeability and practical uses as molecule filter and nanosolid filter. The test of the membrane with pure water reveals that the membrane possesses a fast permeability while consumes very low energy due to the significantly high porosity. The test of the membrane with 13 nm Au solution and yellow-emitting CdTe QDs reveals that both the nanosolids are completely removed from the solution, indicating the membrane is an efficient nanosolid filter. The high efficiency is because the membrane is free of deficiencies and the flat and broad surfaces of the nanoribbons are ideal permeation barriers. The test of the membrane with charged molecules reveals that cationic species and anionic species are discriminated and at the same time the cationic species are enriched on the membrane, which indicate that the membrane is an ideal molecule filter too. The present work should provide a significant step forward to bringing macroscopic architectures assembled by 1D nanostructure much closer to real-world applications involving isolation and enrichment of biomolecules, catalyst reclamation, environmental remediation, and water purification. More broadly, through the on-demand capture of tiny nanosolids with optical, electrical, magnetic, and/or catalytic functionality, it is able to design and construct novel macroscopic nanocomposites readily; this will extend the applications of the titanate nanoribbon membrane beyond separation to the areas of photoelectrochemical devices, chemical sensors, catalysis, plasmonics, and so on.

Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(µ-S2)].

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(µ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(µ(3)-S)(3)Cu(3)(µ-Cl)}(2)Cu(µ-Cl)(2)(µ(7)-Cl)(MeCN)](2) (3), [{Tp*W(µ(3)-S)(3)Cu(3)}(2)Br(µ-Br)(2)(µ(4)-Br)(MeCN)] (4), and [{Tp*W(µ(3)-S)(3)Cu(3)}(2){Cu(2)(µ-I)(4)(µ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(µ(3)-S)(3)Cu(3)X}(2)(µ-X)(2)(µ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(µ(3)-S)(3)Cu(3)](2+) dications are linked via a µ(7)-Cl(-) bridge, two µ-Cl(-) bridges, and a [Cu(MeCN)(µ-Cl)(2)](+) bridge. For 4, one [Tp*W(µ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(µ(3)-S)(3)Cu(3)Br](+) cation are linked via a µ(4)-Br(-) and two µ-Br(-) bridges. For 5, the two [Tp*W(µ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(µ-I)(2)Cu(µ(3)-I)(2)Cu(µ-I)(2)](4+) species. For 6 and 7, two [Tp*W(µ(3)-S)(3)Cu(3)X](+) cations are linked by a µ(4)-X(-) and two µ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.