Role of intrinsic defects on carbon adsorbent for enhanced removal of Hg^(2+)in aqueous solution

Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollution and easy leaching of active components during use.In this paper,the role of intrinsic defects on Hg^(2+)adsorption for carbon adsorbent was investigated.The maximum adsorbing capacity of defectrich carbon has been improved up to 433 mg·g^(-1)which is comparable to most of the modified carbon adsorbents via supported metal chloride or noble metal components.The basicity is increased with the content of defective sites and the strong chemical bonding can be formed via electron transformation between the defect sites with adsorbed Hg^(2+).The present study gives a direction to explore cheap and easily scale-up high-performance mercury adsorbents by simply tuning the intrinsic defective structure of carbon without the necessity to support metal or other organic compounds.

Densely packed ultrafine SnO_(2) nanoparticles grown on carbon cloth for selective CO_(2) reduction to formate

Electrochemical reduction of CO_(2) to fuels and chemicals is a viable strategy for CO_(2) utilization and renewable energy storage.Developing free-standing electrodes from robust and scalable electrocatalysts becomes highly desirable.Here,dense SnO_(2) nanoparticles are uniformly grown on three-dimensional(3D)fiber network of carbon cloth(CC)by a facile dip-coating and calcination method.Importantly,Zn modification strategy is employed to restrain the growth of long-range order of SnO_(2) lattices and to produce rich grain boundaries.The hybrid architecture can act as a flexible electrode for CO_(2)-to-formate conversion,which delivers a high partial current of 18.8 m A cm-2 with a formate selectivity of 80%at a moderate cathodic potential of-0.947 V vs.RHE.The electrode exhibits remarkable stability over a 16 h continuous operation.The superior performance is attributed to the synergistic effect of ultrafine SnO_(2) nanoparticles with abundant active sites and 3D fiber network of the electrode for efficient mass transport and electron transfer.The sizeable electrodes hold promise for industrial applications.

Effect of fused silica subsurface defect site density on light intensification

The effect of defect density on the modulation of incident laser waves is investigated. First, based on the actual defect distribution in the subsurface of fused silica, a three-dimensional （3D） grid model of defect sites is constructed. The 3D finite-difference time-domain method is developed to solve the Maxwell equations. Then the electrical field intensity in the vicinity of the defect sites in the subsurface of fused silica is numerically calculated. The relationships between the maximal electrical field intensity in fused silica and the geometry of the defect sites are given. The simulated results reveal that the modulation becomes more remarkable with an increase of the defect density. In addition, the effect of the distribution mode of defects on modulation is discussed. Meanwhile, the underlying physical mechanism is analyzed in detail.

Fabrication of highly effective electrodes for iron chromium redox flow battery

Iron-chromium redox flow batteries(ICRFBs)have emerged as promising energy storage devices due to their safety,environmental protection,and reliable performance.The carbon cloth(CC),often used in ICRFBs as the electrode,provides a suitable platform for electrochemical processes owing to its high surface area and interconnected porous structure.However,the CC electrodes have issues,such as,insufficient electron transfer performance,which limits their industrial application.Here,we employed silicic acid etching to carve dense nano-porous structures on the surface of CC electrodes based on the favorable design of ICRFBs and the fundamental principles of electrode polarization losses.As a result,we developed a multifunctional carbon cloth electrode with abundant vacancies,notably enhancing the performance of the battery.The fabricated electrode showcased a wealth of defect sites and superior electronic transport properties,offering an extensive and effective reaction area for rapidly flowing electrolytes.With an electrode compression ratio of 40%and the highest current density in ICRFBs so far(140 mA·cm^(-2)),the battery achieved the average energy efficiency of 81.3%,11.24%enhancement over the previously published work.Furthermore,throughout 100 charge-discharge cycles,the average energy efficiency degradation was negligible(~0.04%),which has the potential to become the most promising candidate for large-scale and long-term electrochemical energy storage applications.

Ir-Pd nanoalloys with enhanced surface-microstructure-sensitive catalytic activity for oxygen evolution reaction in acidic and alkaline media

Ir-based dectrocatalysts have been system- atically studied for a variety of applications, among which the electrocatalysis for oxygen evolution reaction （OER） is one of the most prominent. The investigation on surface-micro- structure-sensitive catalytic activity in different pH media is of great significance for developing efficient electrocatalysts and corresponding mechanism research. Herein, shape-tunable Ir- Pd alloy nanocrystals, including nano-hollow-spheres （NHSs）, nanowires （NWs）, and nanotetrahedrons （NTs）, are synthe- sized via a facile one-pot solvothermal method, Electro- chemical studies show that the OER activity of the Ir-Pd alloy nanocatalysts exhibits surface-microstructure-sensitive en- hancement in acidic and alkaline media. Ir-Pd NWs and NTs show more than five times higher mass activity than com- mercial Ir/C catalyst at an overpotential of 0.25 V in acidic and alkaline media. Post-XPS analyses reveal that surface Ir（VI） oxide generated at surface defective sites of Ir-Pd nanocata- lysts is a possible key intermediate for OER. In acidic medium, the specific activity of Ir-Pd nanocatalysts has a positive cor- relation with the surface roughness of NWs 〉 NHSs 〉 NTs. However, the strong dissociation of surface Ir（VI） species （IrO42-） at surface defective sites is a possible obstacle for the formation of Ir（VI） oxide, which reverses the activity sequence for OER in alkaline medium.

Biochar aerogel-based electrocatalyst towards efficient oxygen evolution in acidic media

The controllable synthesis of oxygen evolution reaction(OER)electrocatalyst is an urgent need to advance the develop-ment of sustainable energy conversion and storage.However,the OER efficiency in acidic media is seriously hindered by slow reaction kinetics.The traditional acidic OER electrocatalysts are more prone to be oxidized and corroded as results of unstable carrier structures and variable electronic states of active species.Herein,a high-performing biochar aerogel(BA)based electrocatalyst were realistically designed and synthetized via joint utilization of the terrestrial lignin and seaweed polysaccharide as carbon sources.Originating from the induction effect of"egg-box"structure in alginate and the self-template effect of lignosulfonate,the BA decorated with Ru/RuS_(2)particles was synthesized triumphantly.The as-synthesized electrocatalyst required a low overpotential of 228 mV to attain 10 mA cm^(−2)in 0.5 M H_(2)SO_(4)and exhibited a good stability for over 12,000 s.The good activity was strongly dependent on the assembled unique two-dimensional/three-dimensional(2D/3D)channels in carbon aerogels.Notably,the numerous defective sites at carbon could strongly interact with the Ru/RuS_(2)heterojunction for remarkably enhancing the catalytic activity and stability of whole catalytic system in acidic media.This work puts forward a novel and effective strategy towards the enhancement of the acidic OER process by rational regu-lations of the BA and the coupling effect in micro-interface.

Photocatalytic activity of Eu-doped ZnO prepared by supercritical antisolvent precipitation route:When defects become virtues

The aim of this work is to determine the structural and optical properties of Eu-doped ZnO powders prepared by supercritical antisolvent precipitation route(SAS)and to correlate the physico-chemical features with the photocatalytic activity under UV light.Raman and EPR spectroscopy highlight the introduction of novel defects(mainly singly and doubly ionized oxygen vacancies,and oxygen interstitials)on the Eu-doped ZnO samples,which confer higher hydrophilicity to the doped samples with respect to bare ZnO,as evidenced by FT-IR analysis.Additionally,photoluminescence spectra show that the presence of Eu^(3+) totally quenches the visible light emission typical of bare ZnO,which mainly results from the recombination of photogenerated holes at defective sites.The prepared samples were tested both for the photocatalytic degradation of crystal violet dye(CV)and for the partial oxidation of ferulic acid under UV irradiation.The photocatalytic activity results evidence of a higher ability of Eu-doped photocatalysts to degrade CV and ferulic acid,while higher selectivity values towards vanillin are obtained in the presence of bare ZnO.The higher activity of Eu-doped ZnO photocatalysts is linked to the stabilization of photogenerated holes and to their higher hydrophilicity,both brought by the generation of defective sites induced by the presence of Eu^(3+) ions within the ZnO lattice.

Directional design and synthesis of high-yield hollow Fe-MFI zeolite encapsulating ultra-small Fe_(2)O_(3) nanoparticles by using mother liquid

How to directionally design the hollow zeolite via a green route is of great significance. Here, we successfully synthesized the hollow Fe-silicate-1 encapsulated ultra-small Fe_(2)O_(3) nanoparticles (2.5 nm) with higher yield (85.2%) by mother liquid than traditional dissolution-recrystallization for the first time, which was achieved by precisely regulating the number and distribution of defects in zeolite and cleverly utilizing the TPAOH and nuclei in mother liquor. The effects of synthetic temperature, synthetic period and addition amount of parent zeolite on the formation of hollow zeolite have been investigated and the effect of synthetic conditions on the defects in parent zeolite has been also firstly quantified. The corresponding formation mechanism has been proposed. The abundant inner defects provided by the zeolite synthesized at 130 °C for 1 day and large amount of TPAOH remaining in mother liquid are conducive to the formation of hollow zeolite. Meanwhile, both parent zeolite and nuclei (4-, 5-member rings and structure units) in mother liquid obtained at 130 °C play the crucial roles in enhancing the zeolite yield. Notably, Fe_(2)O_(3) nanoparticles could decompose into small fragments by the interaction with nuclei in mother liquid. Partial ultra-small Fe_(2)O_(3) nanoparticles would be encapsulated in cavity and the rest could be inserted in the zeolite framework, which is significantly different from the conventional dissolution-recrystallization mechanism. The obtained encapsulated catalyst shows the superior catalytic performance and stability in phenol and tetracycline degradation reactions.

Rational tuning of thorium-organic frameworks by reticular chemistry for boosting radionuclide sequestration

The reticular chemistry strategy presents a powerful molecule-design tool to tailor the physical and chemical properties of metal-organic framework(MOF).In this work,we for the first time investigated the effect of organic ligands on the radionuclide sequestration(TcO_(4)^(-))of thorium-organic framework.Through a coordination modulation technique,two novel isoreticular thorium-organic frameworks,namely Th-MOF-67 and Th-MOF-68,were obtained.Relative to the antetype MOF of Th-MOF-66 that shows extremely low uptake of ReO_(4)^(-)(a chemical surrogate of radioactive TcO_(4)^(-)),the isoreticular MOFs of Th-MOF-67 and Th-MOF-68 enable ultrahigh uptake of ReO_(4)^(-),giving an impressively 36.8-fold or 56-fold enhancement,respectively.The adsorption capacity of Th-MOF-68 is as high as 560 mg/g,exceeding most reported adsorbents for such use.The mechanism for such exceptional outstanding performance,as unveiled by both the single crystal X-ray diffraction and theoretical calculation,is due to coordination interaction for Th-MOF-67,when a tetrazolate ligand was used,or a combined effect from both coordination interaction and anion-exchange for Th-MOF-68,if using a triazolate ligand.