Solvation Effect-Determined Mechanisms of Cation Exchange Reactions for Efficient Multicomponent Nanocatalysts.

Cation exchange (CE) reaction is a classical synthesis method for creating complex structures. A lock of study on intrinsic mechanism limits its understanding and practical application. Using X-ray absorption spectroscopy, we observed that the evolution from Ru-Cl to Ru-O/OH occurs during the CE between K2RuCl6 and CoSn(OH)6 in aqueous solution, while CE between K2PtCl6 and CoSn(OH)6 is inhibited due to the failure of structural evolution from Pt-Cl to Pt-O/OH. Theoretical simulations imply that the interaction between Ru-O and CoSn(OH)6 with Co vacancy (CoVCoSn(OH)6) endows the electron transfer, as a result of strengthened adsorption on CoVCoSn(OH)6. Moreover, this mechanism is validated for CE between K2RuCl6 and ASn(OH)6 (A = Mg, Ca, Mn, Co, Cu, Zn), and CE between K2PdCl6/Na3RhCl6/K2IrCl6 and CoSn(OH)6. Impressively, the Pt-free CoRuSn(OH)x produced via CE displays a mass activity and a power density of 15.0 A mgRu-1 and 11.6 W mgRu-1, respectively, for anion exchange membrane fuel cell (AEMFC) exceeding the values of commercial PtRu/C (11.8 A mgRu+Pt-1 and 9.0 W mgRu+Pt-1). This work, for the first time, reveals the intrinsic mechanism of CE as structural evolution of target ion breaking through the traditional classic etch-adsorption mechanism and will promote fundamental research and practical application in various fields.

Durable Multiblock Poly(biphenyl alkylene) Anion Exchange Membranes with Microphase Separation for Hydrogen Energy Conversion.

Anion exchange membrane fuel cells (AEMFCs) and water electrolysis (AEMWE) show great application potential in the field of hydrogen energy conversion technology. However, scalable anion exchange membranes (AEMs) with desirable properties are still lacking, which greatly hampers the commercialization of this technology. Herein, we propose a series of novel multiblock AEMs based on ether-free poly(biphenyl ammonium-b-biphenyl phenyl)s (PBPA-b-BPPs) that are suitable for use in high performance AEMFC and AEMWE systems because of their well-formed microphase separation structures. The developed AEMs achieved outstanding OH- conductivity (162.2 mS cm-1 at 80 °C) with a low swelling ratio, good alkaline stability, and excellent mechanical durability (tensile strength >31 MPa and elongation at break >147 % after treatment in 2 M NaOH at 80 °C for 3750 h). A PBPA-b-BPP-based AEMFC demonstrated a remarkable peak power density of 2.41 W cm-2 and in situ durability for 330 h under 0.6 A cm-2 at 70 °C. An AEMWE device showed a promising performance (6.25 A cm-2 at 2 V, 80 °C) and outstanding in situ durability for 3250 h with a low voltage decay rate (<28 µV h-1 ). The newly developed PBPA-b-BPP AEMs thus show great application prospects for energy conversion devices.

Application of Nano-Hydroxyapatite Derived from Oyster Shell in Fabricating Superhydrophobic Sponge for Efficient Oil/Water Separation.

The exploration of nonhazardous nanoparticles to fabricate a template-driven superhydrophobic surface is of great ecological importance for oil/water separation in practice. In this work, nano-hydroxyapatite (nano-HAp) with good biocompatibility was easily developed from discarded oyster shells and well incorporated with polydimethylsiloxane (PDMS) to create a superhydrophobic surface on a polyurethane (PU) sponge using a facile solution-immersion method. The obtained nano-HAp coated PU (nano-HAp/PU) sponge exhibited both excellent oil/water selectivity with water contact angles of over 150° and higher absorption capacity for various organic solvents and oils than the original PU sponge, which can be assigned to the nano-HAp coating surface with rough microstructures. Moreover, the superhydrophobic nano-HAp/PU sponge was found to be mechanically stable with no obvious decrease of oil recovery capacity from water in 10 cycles. This work presented that the oyster shell could be a promising alternative to superhydrophobic coatings, which was not only beneficial to oil-containing wastewater treatment, but also favorable for sustainable aquaculture.

Photosynergetic Electrochemical Synthesis of Graphene Oxide.

Here we propose a strategy of radical oxidation reaction for the high-efficiency production of graphene oxide (GO). GO plays important roles in the sustainable development of energy and the environment, taking advantages of oxygen-containing functional groups for good dispersibility and assembly. Compared with Hummers' method, electrochemical exfoliation of graphite is considered facile and green, although the oxidation is fairly low. To synthesize GO with better crystallinity and higher oxidation degree, we present a photosynergetic electrochemical method. By using oxalate anions as the intercalation ions and co-reactant, the interfacial concentration of hydroxyl radicals generated during electrochemical exfoliation was promoted, and the oxidation degree was comparable with that of GO prepared by Hummers' method. In addition, the crystallinity was improved with fewer layers and larger size. Moreover, the aniline coassembled GO membrane was selectively permeable to water molecules by the hydrogen-bond interaction, but it was impermeable to Na+, K+, and Mg2+, due to the electrostatic interactions. Thus, it has a prospective application to water desalination and purification. This work opens a novel approach to the direct functionalization of graphene during the electroexfoliation processes and to the subsequent assembly of the functionalized graphene.

Well-dispersed TiO2 nanoparticles anchored on Fe3O4 magnetic nanosheets for efficient arsenic removal.

Magnetic iron-titanium binary oxide as an effective adsorbent for arsenic contaminant is a challenge primarily because of their bulk structure and agglomeration effect. Herein, a novel and uniform sandwich-like magnetic Fe3O4@TiO2 sheets were synthesized by utilizing a facile strategy involving amorphous-to-crystalline transformation and reduction in H2, to achieve dispersed anatase TiO2 nanoparticles with a small size of ∼8 nm anchored on Fe3O4 sheets. The resultant Fe3O4@TiO2 sheets nanocomposite possessing a high specific surface area of ∼89.4 m2 g-1 and available magnetic susceptibility of ∼20.0 emu g-1, significantly enhanced the photocatalytic oxidation property of arsenite and considerable adsorption capability for arsenic removal. The adsorption capacities of As(V) and As(III) with UV-assisted from adsorption experimental results were 36.36 and 30.96 mg g-1, respectively, while the residual concentrations for both As(V) and As(III) were lower than the strict limit of 10 µg L-1. Adsorption equilibriums were almost reached within 45 min. In addition, the adsorbent exhibited excellent stability over a broad pH range of 3-9 and still maintained great removal efficiency after five time regeneration cycles. Furthermore, except for silicate and phosphate, the extremely weak inhibiting influences of common co-existing ions in arsenic removal process, demonstrated that the developed magnetic Fe3O4@TiO2 sheets with unique nanostructure could be a promising efficient adsorbent for arsenic removal.

Fabrication of polyamide nanofiltration membrane with tannic acid/poly(sodium 4-styrenesulfonate) network-like interlayer for enhanced desalination performance.

The traditional polyamide composite nanofiltration membranes have high selectivity and low water permeance, so it is necessary to find strategies to raise the permeance. Herein, a novel polyamide nanofiltration membranes with high permeance were fabricated by coating a loose hydrophilic network-like interlayer, where tannic acid (TA) with pentapophenol arm structure binds to poly(4-styrenesulfonate) (PSS) polymer through hydrogen and ionic interactions. The effects of the network-like TA/PSS interlayer on surface morphology, surface hydrophobicity, and the interfacial polymerization mechanism were investigated. The outcomes demonstrated that the TA/PSS interlayer can offer a favorable environment for interfacial polymerization, enhance the hydrophilicity of the substrate membrane, and delay the release of piperazine (PIP). The optimized TFC-2 presents pure water flux of 22.7 ± 2.8 L m-2 h-1 bar-1, Na2SO4 rejection of 97.1 ± 0.5 %, and PA layer thickness of about 38.9 ± 2.5 nm. This provides new strategies for seeking to prepare simple interlayers to obtain high-performance nanofiltration membranes.

Tubular palladium-based catalysts enhancing direct ethanol electrooxidation.

Direct ethanol fuel cell (DEFC) has the advantages of high power density, high energy conversion efficiency and environmental friendliness, but its commercialization is restricted by factors such as insufficient activity and low anti-poisoning ability of anode catalyst for incomplete oxidation of ethanol. It is of great significance to design and prepare anode catalyst with high activity and high anti-poisoning ability that can be recycled. In this work, tubular palladium-based (Pd-based) catalysts with abundant lattice defect sites were prepared by simple and reproducible electro-displacement reactions using Cu nanowires as sacrificial template. Pd is the main catalytic element which provides adsorption sites for ethanol oxidation. Ag and Cu introduced facilitates the formation of hydroxyl groups to oxidize toxicity intermediates, and changes the d-band center position of Pd, so as to adjust the adsorption and desorption of ethanol and its intermediates on the Pd surface. At the same time, Au introduced with high potential maintains the stability of the catalyst structure. The tubular structure exposes more active sites, improves the atomic utilization rate and enhances the ability of the catalyst resisting dissolution and aggregation. The series of PdAuAgCu tubular catalysts with outer layer dendrites were prepared by electro-displacement reactions using the mixture (ethylene glycol : ultra-pure water = 3 : 1) as the reaction solvent and fivefold twinned Cu nanowires as sacrificial template. The performance evaluation of ethanol electrocatalytic oxidation showed that the Pd17Au40Ag11Cu32 tubular catalysts were prepared at 120 °C and 10 mM CTAB had excellent overall performance, with a peak mass activity of 6335 mA mgPd-1, which was 9.6 times of Pd/C (JM). The residual current density after the stability test of 3000 s was 249 mA mgPd-1, which was 3.3 times of Pd/C (JM).

Correlation between the Humidity-Dependent Surface Microstructure and Macroconductivity of Anion Exchange Membranes.

Anion exchange membrane (AEM) fuel cells have gained significant interest in recent years due to their promising applications in cost-effective and environmentally friendly energy conversion. Among various factors that affect their performance, water content plays an important role in the conductivity and stability of AEMs. However, the effect of the hydration level on the microstructure of AEMs and the correlation between the microstructure and macroconductivity have not been systematically investigated. In this work, four AEMs, quaternary ammonia polysulfone, quaternary ammonia poly(N-methyl-piperidine-co-p-terphenyl) (QAPPT), and bromoalkyl-tethered poly(biphenyl alkylene)s PBPA and PBPA-co-BPP, have been studied by atomic force microscopy and electrochemical impedance spectroscopy to elucidate the correlation between the humidity-dependent surface microstructure and macroconductivity of the AEMs. We obtained phase images by atomic force microscopy and identified hydrophilic and hydrophobic domains by fitting the distribution curve of phase images, which reasonably distinguishes hydrophilic domains from hydrophobic domains of the membrane surface, and thus, the surface hydrophilic area ratio and average size could be quantitatively analyzed. The conductivities of the membranes were then measured by electrochemical impedance spectroscopy at various humidities. The joint results from atomic force microscopy and electrochemical measurements help clarify the effect of the hydration level on the microphase separation and ionic conduction of the membranes.

Self-recoverable Pd-Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation.

Self-recoverable Pd-Ru/TiO2 nanocatalysts have been prepared by electrochemical stripping of Pd-Ru/TiO2 precursors. For the ethanol oxidation reaction (EOR), these Pd-Ru/TiO2 nanocatalysts are used as an anode catalyst. The characterization of catalysts via chronoamperometry has been repeated 15 times. After 15 stability tests, the Pd1Ru0.69/TiO2 nanocatalysts still achieve a factor of 9.4 enhancement at the residual current density (309.42 mA mgPd-1) for the EOR over commercial Pd/C catalysts (33.01 mA mgPd-1). From the 5th to 15th test, when each 10 000 s stability test is performed in a fresh ethanol electrolyte, the initial and residual current density of the catalysts could recover to the original or even better value in a few hours before performing another 10 000 s stability test. Herein, these Pd-Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation are self-recoverable. Density functional theory calculations reveal that the introduction of oxophilic metal Ru and a TiO2 support into Pd-based catalysts and the synergistic effects between Ru and TiO2 have led to the ultrastability towards the EOR. The introduction of oxophilic metal Ru and a TiO2 support into catalysts can reduce the adsorption energy of OHads on the Pd-Ru/TiO2 nanocatalysts, and it will inhibit the COads produced and adsorbed on the Pd surface.

Lattice-Defect-Enhanced Adsorption of Arsenic on Zirconia Nanospheres: A Combined Experimental and Theoretical Study.

Zirconium oxide (ZrO2) nanoadsorbents exhibit great potential in the remediation of arsenic-polluted water. However, physicochemical structure-adsorption performance relationship is not well-understood, which retards further development of high-performance ZrO2 nanoadsorbents. Herein, a facile-controlled crystallization strategy was developed to synthesize defective ZrO2 with the assistance of organic ligands. Systematic characterizations showed that this proposed synthesis strategy can be exploited to regulate the defective density of ZrO2, whereas other structural properties remain almost unchanged. Batch adsorption experiments exhibited that UiO-66-SH-A with a higher lattice defect possessed a larger capacity and a faster rate for the uptake of As(III)/As(V). The maximum capacities of UiO-66-SH-A to uptake As(III) and As(V) were up to 90.7 and 98.8 mg/g, respectively, which are 12.3 and 11.5 times larger than those of UiO-66-A. These results from the structure-performance analysis and theoretical calculations further reveal that lattice defect plays a key role in the enhancement of arsenic adsorption on ZrO2. We hope this new understanding of the structure-dependent adsorption performance will provide a valuable insight for designing Zr-based nanoadsorbents to capture arsenic.