NiFe-LDH-Decorated Ti-Doped Hematite Photoanode for Enhancing Solar Water-Splitting Efficiency.

Ti-doped α-Fe2O3 nanorods were prepared by a facile hydrothermal method, followed by a NiFe-LDH catalyst that was electrodeposited on the doped α-Fe2O3 nanorods to structure an integrating photoanode Ti:Fe2O3/NiFe-LDH for improving solar PEC water-splitting efficiency. The structure and properties of electrode materials were characterized and the PEC properties of photoanodes were measured. The results show that the photocurrent density of the photoanode enhances 11.25 times at 1.23 V (vs RHE) and the IPCE value enhances 4.10 times at 420 nm compared with pristine α-Fe2O3. The enhancement is attributed to the separating of photogenerated electron-hole, the increase of carrier density, and the acceleration of the carrier transfer rate due to the dual action of doping and catalysis.

Design and Synthesis of Cobalt-Based Electrocatalysts for Oxygen Reduction Reaction.

Oxygen reduction reaction (ORR) is the crucial step of various renewable energy conversion and storage technologies such as fuel cells and air-batteries. Cobalt-based electrocatalysts including oxides/chalcogenides and Co-Nx /C, one kind of non-precious metal electrocatalysts with competitive activity, enhanced durability, and acceptable cost, have been proposed as the potentially interesting alternatives to Pt-based electrocatalysts. In this account, we summarized the synthesis methods and the corresponding main impact factors including ligand effect, particle size effect, crystal structure, nanostructure, defects and active centers related to the ORR performance on both of oxides/chalcogenides and Co-Nx /C. Some special points have been discussed on design and synthesis of low-cost and high-performance cobalt-based electrocatalysts with enhanced electrocatalytic activity. Also, the current challenges and future trends are proposed for improving the performance of Co-involving electrocatalysts.

Fe(OH)x modified ultra-small Ru nanoparticles for highly efficient hydrogen evolution reaction and its application in water splitting.

Developing highly active electrocatalysts for overall water splitting is of remarkable significance for industrial production of H2. Herein, exceptionally active Fe(OH)x modified ultra-small Ru nanoparticles on Ni(OH)2 nanosheets array (Fe(OH)x-Ru/Ni(OH)2) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are reported. The Fe(OH)x-Ru/Ni(OH)2 nanosheets array prepared with Fe/Ru molar ratio of 5 only requires extremely low overpotentials of 61, 127 and 170 mV to reach current densities of 100, 500 and 800 mA cm-2 in 1 M KOH, respectively, exceeding Pt/C catalyst (75, 160 and 177 mV). Meanwhile, the Fe(OH)x/Ni(OH)2 nanosheets array derived from Fe(OH)x-Ru/Ni(OH)2 exhibits excellent OER activity. It gains current densities of 100, 500 and 800 mA cm-2 at considerably low overpotentials of 265, 285 and 296 mV, respectively, much lower than those of RuO2 and most reported electrocatalysts. The introduction of Fe(OH)x significantly improves the HER activity of Ru nanoparticles by tunning the electronic structure and forming interfaces between Ru and Fe(OH)x. Dramatically, the integrated alkaline electrolyzer based on Fe(OH)x-Ru/Ni(OH)2 and Fe(OH)x/Ni(OH)2 nanosheets array pair just needs 1.649 V to yield a current density up to 500 mA cm-2, exceeding most reported water-splitting electrocatalysts. The strategy reported in this work can be facilely extended to prepare other similar Ru based materials and their derivatives with outstanding catalytic performance for water splitting.

Facile preparation of Au-loaded mesoporous In2O3 nanoparticles with improved ethanol sensing performance.

The in situ monitoring of toxic volatile organic compound gases using metal oxide-based gas sensors is still challenging. Herein, mesoporous In2O3 nanoparticles, assembled using smaller nanoparticles, were synthesized via a facile solvothermal method and used to load Au nanoparticles to prepare mesoporous Au/In2O3 for ethanol detection. The obtained In2O3 and Au/In2O3 were meticulously analysed by XRD, SEM, BET, TEM and XPS techniques. It was revealed that Au nanoparticles were uniformly distributed on mesoporous In2O3 nanoparticles. Notably, the obtained mesoporous 1% Au/In2O3 is highly sensitive to ethanol gas at an optimal working temperature of 180 °C, showing a response of 55 to 50 ppm of ethanol, which is considerably higher compared to that of In2O3 nanoparticles. The significantly enhanced sensitivity results from the electronic and chemical sensitization effects of Au nanoparticles. Moreover, the mesoporous Au/In2O3 nanoparticles also showed eminent selectivity, short response/recovery time, low detection limit, good linear relationship, superb repeatability, and wonderful long-term stability, suggesting that Au/In2O3 nanoparticles have great potential application for in situ monitoring of ethanol gas.

Porous ZnCl2-Activated Carbon from Shaddock Peel: Methylene Blue Adsorption Behavior.

It is of great interest and importance to resource utilization of waste biomass to produce porous carbon for environmental treatments. Pore structure and properties of the obtained carbon mainly relate to carbonization conditions and biomass types. In this work, a series of porous, biomass-activated carbons (AC) were prepared using shaddock peel, with ZnCl2 as a pore-forming agent. The effect of carbonization temperature and the mass ratio between ZnCl2 and shaddock peel were thoroughly investigated. The material composition, surface chemical properties, and surface structures of samples were carefully characterized. The specific surface area and adsorption capacity to methylene blue (MB) of adsorbents were changed with the carbonization temperature and the mass ratios between ZnCl2 and shaddock peel; when the temperature was at 1000 °C and the mass ratio was equal to 2:1, the resulting adsorbent had the largest specific surface area of 2398.74 m2/g and average pore size of 3.04 nm, which showed the highest adsorption capacity to MB to be 869.57 mg/g. The adsorption processes of biomass AC adsorbent matched the pseudo-second-order kinetic model and Langmuir isotherm model. This efficient and environmentally friendly biomass AC adsorbent from shaddock peel, activated by ZnCl2, is a promising candidate for the treatment of water pollution.

Ultra-sensitive ethanol gas sensors based on nanosheet-assembled hierarchical ZnO-In2O3 heterostructures.

Developing efficient sensing materials with super sensitivity and selectivity is imperative to fabricate high-performance gas sensors for satisfying future needs. Herein, we report the preparation of ultrathin nanosheet-assembled 3D hierarchical ZnO/In2O3 heterostructures for the sensitive and selective detection of ethanol by sintering the 3D hierarchical Zn/In glycerolate precursors consisting of ultrathin nanosheets synthesized through a facile solvothermal method. The obtained ZnO/In2O3 heterostructures were carefully characterized by XRD, SEM, HRTEM, BET and XPS. The results showed that the 20%ZnO/In2O3 heterostructure is built up by many ultrathin nanosheets composed of intimately connected ZnO and In2O3 nanoparticles and have a specific surface area as high as 137.1 m2 g-1. Because of the unique hierarchical structure, abundant mesoporous and formation of ZnO-In2O3 n-n heterojunctions, the 20%ZnO/In2O3 heterostructure based sensor was ultra-sensitive to ethanol gas at 240 °C and exhibited a response as high as 170 toward 50 ppm of ethanol, which is about 3.3 times higher than that of pure In2O3 based sensor. Moreover, the sensor based on 20%ZnO/In2O3 heterostructure has virtues of excellent selectivity, good long-term stability and moderate response and recovery speed (35/46 s) toward ethanol. Therefore, the ultrathin nanosheet-assembled 3D hierarchical heterostructures are promising materials for fabricating high-performance gas sensors.

Synthesis of novel BiVO4/Cu2O heterojunctions for improving BiVO4 towards NO2 sensing properties.

To develop a high sensitive and low temperature NO2 gas sensor, the novel BiVO4/Cu2O heterojunctions were synthesized by a modified metal organic decomposition method to decorate BiVO4 nanoplates using Cu2O nanoparticles for enhancement of BiVO4 sensing performance to NO2. The structure and morphology of BiVO4, Cu2O and BiVO4/Cu2O composites were characterized by XRD, SEM and TEM spectra. The results indicate that the BiVO4/Cu2O heterojunctions are composed of monoclinic BiVO4 nanoplates with the thickness about 1.0-1.2 µm and 30-40 nm diameters of cubic Cu2O nanoparticles. The gas-sensing tests display that the composite exhibits rapid and linear responses to low concentration NO2 (from 100 ppb to 8.0 ppm), the highest response reaches 4.2 towards 4 ppm NO2 at 60 °C and relative humidity of 28.3%, which is more than 2 times of pure BiVO4 at the same condition. The enhanced sensing properties benefit from the novel p-n heterojunction between BiVO4 and Cu2O, which forms a depletion layer at the interface, leading to resistance increase of composites in NO2. The work demonstrates the as-synthesized BiVO4/Cu2O is a promising sensing material to detect NO2 gas.

UV absorber co-intercalated layered double hydroxides as efficient hybrid UV-shielding materials for polypropylene.

Two kinds of UV absorbers 2-hydroxy-4-methoxy-benzophenone-5-sulphonic acid (HMBA) and cinnamic acid (CA) were successfully co-intercalated into the interlayer of Mg2ZnAl layered double hydroxides (LDH) by a modified coprecipitation method to prepare novel UV-shielding material HMBA-CA-LDH for improving the anti-photoaging capability of polypropylene (PP). The characterization results reveal the presence of host-guest interactions between the LDH host layers and HMBA/CA guest anions as well as guest-guest interactions between guest anions in HMBA-CA-LDH, and the HMBA-CA-LDH has much stronger UV absorption capability than the HMBA intercalated LDH (HMBA-LDH) in the whole UV band and a much broader UV absorption band than the CA intercalated LDH (CA-LDH). A series of LDH/PP composites with evenly dispersed LDH nanosheets were prepared by incorporating the prepared LDHs into the matrix of PP via the solvent casting method. As expected, LDH/PP composites show higher thermal stability and better anti-photoaging ability than pristine PP. Interestingly, HMBA-CA-LDH/PP shows better anti-photoaging performance in comparison with HMBA-LDH/PP and CA-LDH/PP because of its better UV-shielding ability arising from the synergistic UV-shielding effects of both HMBA and CA, and the HMBA-CA-LDH can reduce the photodegradation of PP by about 85%. Hence, the prepared novel HMBA-CA-LDH has potential application in the field of PP as an efficient and promising UV-shielding material.

Recent Progress on Adsorption Materials for Phosphate Removal.

BACKGROUND: High concentration of phosphate has been threatening human health and the ecosystem. Adsorption is one of high-efficiency and low-cost techniques to reduce the concentration of phosphate. This mini review aims to summarize the recent development of adsorption materials for phosphate removal. METHOD: We conducted a detailed search of "adsorption of phosphate" in the published papers and the public patents on the adsorbents for phosphate based on Web of Science database in the period from January 1 2012 to December 31 2017. The corresponding literature was carefully evaluated and analyzed. RESULTS: One hundred and forty one papers and twenty two recent patents were included in this review. An increased trend in scientific contributions was observed in the development of adsorption materials for phosphate removal. Three kinds of promising adsorbents: layered double hydroxides, natural materials, and metal oxides were paid special attention including removal mechanism, performance as well as the relationship between adsorption performance and structure. Both the chemical composition and the morphology play a key role in the removal capacity and rate. CONCLUSION: The findings of this review confirm the importance of phosphate removal, show the development trend of high-performance and low-cost adsorption materials for phosphate removal, and provide a helpful guide to design and fabricate high-efficiency adsorbents.

Carbon fiber paper@MgO films: in situ fabrication and high-performance removal capacity for phosphate anions.

Porous magnesium oxide (MgO) films on carbon fiber paper (CF) have been successfully fabricated in a hydrothermal route at different calcination temperatures. The CF@MgO samples (CF@MgO-300, -400, and -500) show different morphologies with the increasing surface area from 3 for CF to 27 m2 g-1 for CF@MgO-400. Among the four investigated samples, the CF@MgO-400 exhibits the highest phosphate removal ability (~ 1230 mg g-1) with promising applications for the large-scale utilization at low cost.

Co-intercalated layered double hydroxides as thermal and photo-oxidation stabilizers for polypropylene.

An elegant and efficient approach consisting in the co-intercalation of stabilizing molecular anions is described here. The thermal stabilizer calcium diethyl bis[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate] (Irganox 1425, MP-Ca) and a photo-oxidation stabilizer (hindered amine light stabilizer, HALS) are co-intercalated into the interlayer regions of layered double hydroxides (LDH) in a one-step coprecipitation. These hybrid organic-inorganic materials are successively dispersed in polypropylene to form H n M n '-Ca2Al/PP composite films (with H = HALS and M = MP) through a solvent casting method. The corresponding crystalline structure, chemical composition, morphology as well as the resistance against thermal aging and photo-oxidation are carefully investigated by various techniques. The results show that the powdered H n M n '-Ca2Al-LDHs hybrid materials have a much higher thermal stability than MP-Ca and HALS before intercalation. In addition, the H n M n '-Ca2Al/PP composites exhibit a higher overall resistance against thermal degradation and photo-oxidation compared to LDHs intercalated with only HALS or MP. This underlines the benefit of the co-intercalation. The co-intercalated LDH materials pave a new way in designing and fabricating high-performance multifunctional additives for polymers.

Micrometer-sized dihydrogenphosphate-intercalated layered double hydroxides: synthesis, selective infrared absorption properties, and applications as agricultural films.

High-performance heat-retention agents for multifunctional green agricultural films are today largely suitable to increase the production yield as well as to save energy. Here, an adapted ammonia releasing hydrothermal method was used to produce a series of micrometer-sized carbonate-layered double hydroxide (CO3-LDH) precursors of sizes ranging from 1.32 µm to 8.64 µm by simply adjusting the feeding Mg2+ concentration from 0.80 mol L-1 to 0.20 mol L-1. From these pristine LDH materials, µm-sized dihydrogenphosphate-intercalated LDHs (H2PO4-LDHs) were prepared by an anion-exchange method. The structure, the platelet size, and the associated selective IR absorption properties of the H2PO4-LDH and the derivative H2PO4-LDH/EVA composite as well as the related visible transmittance and the photostability of the H2PO4-LDH/EVA film were investigated. The results show that the selective IR absorption in the wavelength range of 7-14 µm enabling the heat retention of the H2PO4-LDHs and H2PO4-LDH/EVA composites depends on the corresponding number-averaged particle size of H2PO4-LDH in the range of 2.01 µm to 8.80 µm. Compared with EVA, the H2PO4-LDH/EVA composites demonstrate a significant improvement of selective IR absorption, while maintaining acceptable visible transmittance, and similar photostability. An optimized particle size of H2PO4-LDH of ca. 5.85 µm leads to 60% selective IR absorption and 64% selective IR absorption when dispersed in EVA, while the polymer free of filler exhibits less than 50% absorption in the 7-14 µm IR domain.

Superb removal capacity of hierarchically porous magnesium oxide for phosphate and methyl orange.

Here, we successfully developed a template-free way to fabricate hierarchically porous magnesium oxide (MgO) and carefully investigated the adsorption behavior for phosphate and methyl orange (MO). The average pore size and the percentage porosity decreased with the increase in the feeding ratio of Mg2+/NH3. Among the three samples, MgO-25 shows the highest surface area of 63 m2 g-1 determined by the mercury intrusion method, and MgO-50 exhibits the highest BET surface area of 121 m2 g-1. For all the MgO samples, the adsorption process follows the pseudo second-order and Langmuir isotherm for phosphate, while pseudo second-order and the Freundlich isotherm for MO. Among the investigated samples, MgO-25 shows the most maximum removal capacity of 478.5 mg g-1 for phosphate and the highest removal capacity of 4483.9 mg g-1 for MO. This study compromises a low-cost and convenient dual function material for excellent water remediation of multiple industries.

Novel Carbon Paper@Magnesium Silicate Composite Porous Films: Design, Fabrication, and Adsorption Behavior for Heavy Metal Ions in Aqueous Solution.

It is of great and increasing interest to explore porous adsorption films to reduce heavy metal ions in aqueous solution. Here, we for the first time fabricated carbon paper@magnesium silicate (CP@MS) composite films for the high-efficiency removal of Zn2+ and Cu2+ by a solid-phase transformation from hydromagnesite-coated CP (CP@MCH) precursor film in a hydrothermal route and detailedly examined adsorption process for Zn2+ and Cu2+ as well as the adsorption mechanism. The suitable initial pH range is beyond 4.0 for the adsorption of the CP@MS to remove Zn2+ under the investigated conditions, and the adsorption capacity is mainly up to the pore size of the porous film. The composite film exhibits excellent adsorption capacity for both of Zn2+ and Cu2+ with the corresponding maximum adsorption quantity of 198.0 mg g-1 for Zn2+ and 113.5 mg g-1 for Cu2+, which are advantageous over most of those reported in the literature. Furthermore, the adsorption behavior of the CP@MS film follows the pseudo-second-order kinetic model and the Langmuir adsorption equation for Zn2+ with the cation-exchange mechanism. Particularly, the CP@MS film shows promising practical applications for the removal of heavy metal ions in water by an adsorption-filtration system.

Fabrication and Adsorption Behavior of Magnesium Silicate Hydrate Nanoparticles towards Methylene Blue.

Magnesium silicate as a high-performance adsorption material has attracted increasing attention for the removal of organic dye pollution. Here, we prepared a series of magnesium silicate hydrates (MSH) in a hydrothermal route, and carefully investigated the corresponding adsorption behavior towards methylene blue (MB) as well as the effect of surface charge on adsorption capacity. The results show that surface charge plays a key role in the adsorption performance of MSH for MB, a negative surface charge density follows the increase of Si/Mg feeding ratio from 1.00 to 1.75, and furthermore the higher negative charge favors the improvement of the adsorption capacity. Among four investigated samples (MSH = 1.00, 1.25, 1.50, and 1.75), MSH-1.75 has the highest negative surface charge and shows the largest adsorption capacity for MB. For example, the equilibrium adsorption quantity is 307 mg·g−1 for MSH-1.75, which is 35% higher than that of 227 mg·g−1 for MSH-1.00. Besides, for MSH-1.75, the as-prepared sample with negative charge exhibits ca. 36% higher adsorption quantity compared to the sample at the zero point of charge (pHZPC). Furthermore, magnesium silicate hydrate material with Si/Mg feeding ratio = 1.75 demonstrates the promising removal efficiency of beyond 98% for methylene blue in 10 min, and the maximum adsorption capacity of 374 mg·g−1 calculated from the Langmuir isotherm model.

Electrocatalytic Cobalt Nanoparticles Interacting with Nitrogen-Doped Carbon Nanotube in Situ Generated from a Metal-Organic Framework for the Oxygen Reduction Reaction.

A metal organic framework (MOF), synthesized from cobalt salt, melamine (mela), and 1,4-dicarboxybezene (BDC), was used as precursor to prepare Co/CoNx/N-CNT/C electrocatalyst via heat treatment at different temperature (700-900 °C) under nitrogen atmosphere. Crystallites size and microstrain in the 800 °C heat-treated sample (MOFs-800) were the lowest, whereas the stacking fault value was the highest among the rest of the homemade samples, as attested to by the Williamson-Hall analysis, hence assessing that the structural or/and surface modification of Co nanoparticles (NPs), found in MOFs-800, was different from that in other samples. CNTs in MOFs-800, interacting with Co NPs, were formed on the surface of the support, keeping the hexagonal shape of the initial MOF. Among the three homemade samples, the MOF-800 sample, with the best electrocatalytic performance toward oxygen reduction reaction (ORR) in 0.1 M KOH solution, showed the highest density of CNTs skin on the support, the lowest ID/IG ratio, and the largest N atomic content in form of pyridinic-N, CoNx, pyrrolic-N, graphitic-N, and oxidized-N species. Based on the binding energy shift toward lower energies, a strong interaction between the active site and the support was identified for MOFs-800 sample. The number of electron transfer was 3.8 on MOFs-800, close to the value of 4.0 determined on the Pt/C benchmark, thus implying a fast and efficient multielectron reduction of molecular oxygen on CoNx active sites. In addition, the chronoamperometric response within 24 000 s showed a more stable current density at 0.69 V/RHE on MOFs-800 as compared with that of Pt/C.

Co-intercalation of Acid Red 337 and a UV absorbent into layered double hydroxides: enhancement of photostability.

Organic-inorganic hybrid pigments with enhanced thermo- and photostability have been prepared by co-intercalating C.I. Acid Red 337 (AR337) and a UV absorbent (BP-4) into the interlayer of ZnAl layered double hydroxides through a coprecipitation method. The obtained compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermogravimetric-differential thermal analysis, UV-visible spectroscopy, and the International Commission on Illumination (CIE) 1976 L*a*b* color scales. The results show the successful co-intercalation of AR337 and BP-4 into the interlayer region of layered double hydroxides (LDHs) and reveal the presence of host-guest interactions between LDH host layers and guest anions of AR337 and BP-4 and guest-guest interactions between AR337 and BP-4. The intercalation can improve the thermostability of AR337 due to the protection of LDH layers. Moreover, the co-intercalation of AR337 and BP-4 not only markedly enhances the photostability of AR337 but also significantly influences the color of the hybrid pigment.

Synthesis and applications of layered double hydroxides based pigments.

Layered double hydroxides (LDHs) have attracted a great deal of attention owing to their structural anisotropy, anion-exchange capability and compositional flexibility and have been widely investigated as catalysts, adsorbents, anion-exchangers, polymer additives, optical materials, and so on. The intercalation of chromophores into the interlayer galleries of LDHs has drawn considerable interest since it can result in a kind of functional pigments showing different photophysical and photochemical properties from the pristine chromophores due to the host-guest and guest-guest interactions. This paper reviews recent patents progress made for the synthesis and applications of LDHs based pigments. The potentional applications and the future development are also discussed.

Layered double hydroxides as flame retardant and thermal stabilizer for polymers.

Layered double hydroxides (LDH) has wide applications as non-toxic and halogen-free flame retardant for various resins and highly efficient thermal stabilizer for halogen-containing polymers. This review will discuss some public patents and relevant papers on the flame retardancy and the thermal stability of LDH/polymer composites when the LDHs with different chemical compositions are used as the additive in the polymer matrix. We have summarized these related LDHs in two tables: one for flame retardant and the other for thermal stabilizer.