Zhe Xu

A new combined process for efficient removal of Cu(II) organic complexes from wastewater: Fe(III) displacement/UV degradation/alkaline precipitation

Efficient removal of heavy metals complexed with organic ligands from water is still an important but challenging task now. Herein, a novel combined process, i.e., Fe(III)-displacement/UV degradation/alkaline precipitation (abbreviated as Fe(III)/UV/OH) was developed to remove copper-organic complexes from synthetic solution and real electroplating effluent, and other processes including alkaline precipitation, Fe(III)/OH, UV/OH were employed for comparison. By using the Fe(III)/UV/OH process, some typical Cu(II) complexes, such as Cu(II)-ethylenediaminetetraacetic acid (EDTA), Cu(II)-nitrilotriacetic acid (NTA), Cu(II)-citrate, Cu(II)-tartrate, and Cu(II)-sorbate, each at 19.2 mg Cu/L initially, were efficiently removed from synthetic solution with the residual Cu below 1 mg/L. Simultaneously, 30-48% of total organic carbon was eliminated with exception of Cu(II)-sorbate. Comparatively, the efficiency of other processes was much lower than the Fe(III)/UV/OH process. With Cu(II)-citrate as the model complex, the optimal conditions for the combined process were obtained as: initial pH for Fe(III) displacement, 1.8-5.4; molar ratio of [Fe]/[Cu], 4:1; UV irradiation, 10 min; precipitation pH, 6.6-13. The mechanism responsible for the process involved the liberation of Cu(II) ions from organic complexes as a result of Fe(III) displacement, decarboxylation of Fe(III)-ligand complexes subjected to UV irradiation, and final coprecipitation of Cu(II) and Fe(II)/Fe(III) ions. Up to 338.1 mg/L of Cu(II) in the electroplating effluent could be efficiently removed by the process with the residual Cu(II) below 1 mg/L and the removal efficiency of ∼99.8%, whereas direct precipitation by using NaOH could only result in total Cu(II) removal of ∼8.6%. In addition, sunlight could take the place of UV to achieve similar removal efficiency with longer irradiation time (90 min).

Enhanced debromination of 4-bromophenol by the UV/sulfite process: Efficiency and mechanism

Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol (4-BP) by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH (6.1-10) and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.

Adjusting the Crystallinity of Mesoporous Spinel CoGa2O4 for Efficient Water Oxidation

Effective and stable electrocatalysts (ECs) are of great importance for the modification of semiconductor (SC) photoanodes, to achieve efficient photoelectrochemical (PEC) water splitting. Herein we demonstrate that the low-crystallinity mesoporous spinel CoGa2O4 oxygen evolution catalyst (OEC), exhibiting excellent bulk electrocatalytic stability and activity for oxygen-evolving reaction (OER), obviously improved water oxidization on a-Fe2O3 photoanode. Low crystallinity not only balances the stability and activity for ECs themselves but facilitates formation of adjustable Schottky junctions between ECs and SCs. Those would contribute to surface state passivation and photogenerated hole extraction, leading to lower onset potential and larger photocurrent. Thus, our finding suggests that low crystallinity could serve as a beneficial feature of ECs to achieve efficient PEC water splitting, owing to its preponderant tendency for the improvement of interface reaction kinetics.

Interface Manipulation to Improve Plasmon-Coupled Photoelectrochemical Water Splitting on α-Fe2O3 Photoanodes

The plasmon resonance effect of metal nanoparticles (NPs) offers a promising route to improve the solar energy conversion efficiency of semiconductors. In this study, it is revealed that hot electrons generated by the plasmon resonance effect of Au NPs tend to inject into the surface states instead of the conduction band of Fe2 O3 photoanodes, and then severe surface recombination occurs. Such an electron-transfer process seems to be independent of external applied potentials, but is sensitive to metal-semiconductor interface properties. Passivating the surface states of Fe2 O3 with a noncatalytic Al2 O3 layer can construct an effective resonant energy-transfer interface between Ti-doped Fe2 O3 (Ti-Fe2 O3 ) and Au NPs. In such a Ti-Fe2 O3 /Al2 O3 /Au electrode configuration, the enhanced photoelectrochemical (PEC) water-splitting performance can be attributed to the following two factors: 1)u2005in the non-light-responsive wavelength range of Au NPs, both the relaxing Fermi pinning effect of the Al2 O3 passivation layer and the higher work function of Au enlarge band bending; thus promoting the charge separation; and 2)u2005in the light-responsive wavelength range of Au NPs, the effective resonant energy transfer contributes to light harvesting and conversion. The interface manipulation proposed herein may provide a new route to design efficient plasmonic PEC devices for energy conversion.

Balancing Catalytic Activity and Interface Energetics of Electrocatalyst-Coated Photoanodes for Photoelectrochemical Water Splitting

For photoelectrochemical (PEC) water splitting, the interface interactions among semiconductors, electrocatalysts, and electrolytes affect the charge separation and catalysis in turn. Here, through the changing of the bath temperature, Co-based oxygen evolution catalysts (OEC) with different crystallinities were electrochemically deposited on Ti-doped Fe2O3 (Ti-Fe2O3) photoanodes. We found: (1) the OEC with low crystallinity is highly ion-permeable, decreasing the interactions between OEC and photoanode due to the intimate interaction between semiconductor and electrolyte; (2) the OEC with high crystallinity is nearly ion-impermeable, is beneficial to form a constant buried junction with semiconductor, and exhibits the low OEC catalytic activity; and (3) the OEC with moderate crystallinity is partially electrolyte-screened, thus contributing to the formation of ideal band bending underneath surface of semiconductor for charge separation and the highly electrocatalytic activity of OEC for lowering over-potentials of water oxidation. Our results demonstrate that to balance the water oxidation activity of OEC and OEC-semiconductor interface energetics is crucial for highly efficient solar energy conversion; in particular, the energy transducer is a semiconductor with a shallow or moderate valence-band level.

Efficient removal of Cr(III)-organic complexes from water using UV/Fe(III) system: Negligible Cr(VI) accumulation and mechanism

Most available processes are incapable of removing Cr(III)-organic complexes from water due to their high solubility, extremely slow decomplexation rate, and possible formation of more toxic Cr(VI) during oxidation. Herein, we proposed a new combined process, i.e., UV/Fe(III) followed by alkaline precipitation (namely UV/Fe(III)+OH), to achieve highly efficient and environmentally benign removal of Cr(III)-organic complexes from water. The combined process could remove Cr(III)-citrate from 10.4xa0mg Cr/L to 0.36xa0mg Cr/L and ∼60% total organic carbon as well. More attractively, negligible Cr(VI) (<0.06xa0mg/L) was formed during the process. In the viewpoint of mechanism, the added Fe(III) generates ·OH radicals to transform Cr(III) into Cr(VI) and simultaneously released the citrate ligand to form Fe(III)-citrate simultaneously. Then, the photolysis of Fe(III)-citrate under UV irradiation involved the citrate degradation and the production of massive Fe(II) species, which in turn transformed the formed Cr(VI) back to Cr(III). The free metal ions, including Cr(III), Fe(II) and Fe(III) were removed by the subsequent alkaline precipitation. Also, the combined process is applicable to other Cr(III) complexes with EDTA, tartrate, oxalate, acetate. The applicability of the combined process was further demonstrated by treating two real tanning effluents, resulting in the residual Cr(III) below 1.5xa0mg/L (the discharge standard of China) and negligible formation of Cr(VI) (<0.004xa0mg/L) as well. In general, the combined process has a great potential for efficient removal of Cr(III) complexes from contaminated waters.

In-Situ Formed Hydroxide Accelerating Water Dissociation Kinetics on Co3N for Hydrogen Production in Alkaline Solution

Sluggish water dissociation kinetics on nonprecious metal electrocatalysts limits the development of economical hydrogen production from water-alkali electrolyzers. Here, using Co3N electrocatalyst as a prototype, we find that during water splitting in alkaline electrolyte a cobalt-containing hydroxide formed on the surface of Co3N, which greatly decreased the activation energy of water dissociation (Volmer step, a main rate-determining step for water splitting in alkaline electrolytes). Combining the cobalt ion poisoning test and theoretical calculations, the efficient hydrogen production on Co3N electrocatalysts would benefit from favorable water dissociation on in-situ formed cobalt-containing hydroxide and low hydrogen production barrier on the nitrogen sites of Co3N. As a result, the Co3N catalyst exhibits a low water-splitting activation energy (26.57 kJ mol-1) that approaches the value of platinum electrodes (11.69 kJ mol-1). Our findings offer new insight into understanding the catalytic mechanism of nitride electrocatalysts, thus contributing to the development of economical hydrogen production in alkaline electrolytes.

Oriented attachment growth of hundred-nanometer-size LaTaON2 single crystals in molten salts for enhanced photoelectrochemical water splitting

Oriented attachment (OA) has been widely used as a term to describe solution-based particle (generally, <10 nm in size) growth proceeding by crystallographic alignment. A big challenge in large-sized crystal growth by the OA crystallization process is the removal of the additives that cause the OA assembling process to occur. Here, we find that the molten salt environment is an ideal medium for OA growth of large-sized inorganic particles without the requirement of any additives. As an example, in Li ion-based molten salts, hundred-nanometer-size LaTaON2 single crystals with no specific morphology can spontaneously assemble into micrometer-size regular crystals. Theoretical and experimental evidence indicated that this OA growth process among the large-sized crystals is governed by a trade-off between electrostatic repulsion and van der Waals attraction, which can be adjusted by the adsorption difference of positive and negative ions on the crystal surface. Finally, due to the significant decrease in charge recombination at grain boundaries, the large single crystal electrode exhibited an enhanced photoelectrochemical performance of 5.1 mA cm−2 at 1.23VRHE, the highest performance among the previously reported LaTaON2 photoanodes. Our findings offer a new approach to assemble large-size single crystals for advanced nanodevices.

Unlocking the potential of graphene for water oxidation using an orbital hybridization strategy

Graphene-based electrocatalytic materials are potential low-cost electrocatalysts for the oxygen evolution reaction (OER). However, substantial overpotentials above thermodynamic requirements limit their efficiency and stability in OER-related energy conversion and storage technologies. Here, we embedded CrN crystals into graphene and in situ electrochemically oxidized them to construct graphene materials with encapsulated Cr6+ ions (Cr6+@G). These Cr6+@G materials exhibit the lowest OER overpotential of 197 mV at 10 mA cm−2 and excellent stability over 200 h at a high current density of about 120 mA cm−2 in an alkaline electrolyte. Spectroscopic and computational studies confirm a stable ion coordination environment significantly benefiting the downshift of the graphene Fermi level via hybridization of C p orbitals with d orbitals of Cr6+ ions that enhances the OER activity and stability.

Molten salt-assisted a-axis-oriented growth of Ta3N5 nanorod arrays with enhanced charge transport for efficient photoelectrochemical water oxidation

Efficiently harvesting light and transporting charges are the main challenges for solar water oxidation by Ta3N5 photoanodes. Herein, we discovered a facile KI molten salt route to fabricate highly oriented Ta3N5 nanorod arrays along the [100] crystallographic direction. The size of the nanorods can be finely tuned by controlling the amount of KI flux due to their bottom-up growth mechanism. The array structure enhances the light scattering, which is beneficial for harvesting more light to make up for the light absorption anisotropy of Ta3N5. The preferred [100] growth orientation guarantees electron migration to the substrate, and the enlarged space charge layer facilitates hole migration to the semiconductor–liquid interface. As a result, under AM 1.5 irradiation, the onset potential of the Ta3N5 nanorod array photoanode reaches 0.65 V versus reversible hydrogen electrode, and the current density reaches 4.65 mA cm−2. The design concept that rationally combines the advantages of charge transport and light utilization may offer a new strategy for efficient solar energy conversion.