Cu1-Fe Dual Sites for Superior Neutral Ammonia Electrosynthesis from Nitrate.

The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3 -) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3 - to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen-containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH-neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3 -. Herein, we constructed a Cu1-Fe dual-site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero-valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3 - removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L-1 NO3 --N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3 - adsorption on Fe sites and strengthened water activation on single-atom Cu sites, decreasing the energy barrier for the rate-determining step of *NO-to-*NOH. This work develops a novel strategy of fabricating dual-site catalysts to enhance the electrosynthesis of NH3 from NO3 -, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment.

Construction of an OCP-ATR-FTIR Spectroscopy Device to In Situ Monitor the Interfacial Reaction of Contaminants: Competitive Adsorption of Cr(VI) and Oxalate on Hematite.

The comprehensive understanding of contaminant interfacial behavior strongly depends on the in situ characterization technique, which is still a great challenge. In this study, we constructed a device integrated with open-circuit potentialand attenuated total reflectance Fourier transform infrared (OCP-ATR-FTIR) spectroscopy to simultaneously monitor the electrochemical and infrared spectral information on the interfacial reaction for the process analysis, taking the competitive adsorption of hexavalent chromium (Cr(VI)) and oxalate on hematite nanocubes (HNC) as an example. The synchronous OCP and infrared results revealed that Cr(VI) interacted with HNC via bidentate binuclear inner-sphere coordination, accompanied by electron transfer from HNC to Cr(VI), while oxalate was adsorbed on HNC through bidentate mononuclear side-on inner-sphere coordination with electron transfer from HNC to oxalate, and also outer-sphere coordination with negative charge accumulation. When oxalate was added to HNC with preadsorbed Cr(VI), oxalate would occupy the inner-sphere adsorption sites and thus cause the detaching of preadsorbed Cr(VI) from HNC. This study provides a promising in situ characterization technique for real-time interfacial reaction monitoring and also sheds light on the competitive adsorption mechanism of oxalate and Cr(VI) on the mineral surface.

Electrochemical removal of ammonium nitrogen in high efficiency and N2 selectivity using non-noble single-atomic iron catalyst.

Ammonia nitrogen (NH4+-N) is a ubiquitous environmental pollutant, especially in offshore aquaculture systems. Electrochemical oxidation is very promising to remove NH4+-N, but suffers from the use of precious metals anodes. In this work, a robust and cheap electrocatalyst, iron single-atoms distributed in nitrogen-doped carbon (Fe-SAs/N-C), was developed for electrochemical removal of NH4+-N from in wastewater containing chloride. The Fe-SAs/N-C catalyst exhibited superior activity than that of iron nanoparticles loaded carbon (Fe-NPs/N-C), unmodified carbon and conventional Ti/IrO2-TiO2-RuO2 electrodes. And high removal efficiency (> 99%) could be achieved as well as high N2 selectivity (99.5%) at low current density. Further experiments and density functional theory (DFT) calculations demonstrated the indispensable role of single-atom iron in the promoted generation of chloride derived species for efficient removal of NH4+-N. This study provides promising inexpensive catalysts for NH4+-N removal in aquaculture wastewater.

An Electrochemical Strategy for Simultaneous Heavy Metal Complexes Wastewater Treatment and Resource Recovery.

Heavy metals chelated with coexisting organic ligands in wastewater impose severe risks to public health and the ambient ecosystem but are also valuable metal resources. For sustainable development goals, the treatment of heavy metal complexes wastewater requires simultaneous metal-organic bond destruction and metal resource recovery. In this study, we demonstrated that a neutral pH electro-Fenton (EF) system, which was composed of an iron anode, carbon cloth cathode, and sodium tetrapolyphosphate electrolyte (Na6TPP), could induce a successive single-electron activation pathway of molecular oxygen due to the formation of Fe(II)-TPP complexes. The boosted •OH generation in the Na6TPP-EF process could decomplex 99.9% of copper ethylene diamine tetraacetate within 8 h; meanwhile, the released Cu ions were in situ deposited on the carbon cloth cathode in the form of Cu nanoparticles with a high energy efficiency of 2.45 g kWh-1. Impressively, the recovered Cu nanoparticles were of purity over 95.0%. More importantly, this neutral EF strategy could realize the simultaneous removal of Cu, Ni, and Cr complexes from real electroplating effluents. This study provides a promising neutral EF system for simultaneous heavy metal complexes wastewater treatment and resource recovery and sheds light on the importance of molecular oxygen activation in the field of pollutant control.

Liquid Nitrogen Activation of Zero-Valent Iron and Its Enhanced Cr(VI) Removal Performance.

In this study, we report that liquid nitrogen treatment is a promising zero-valent iron activation method that does not remove the iron oxide shell; this can improve the apparent Cr(VI) removal rate constant of zero-valent iron by about 4-120 times, depending on the particle sizes and the suppliers of zero-valent iron. It was found that liquid nitrogen, with its low temperature of 77 K, could crack the iron oxide shell of zero-valent iron to produce abundant fractures because of the different thermal expansion coefficients of iron oxide and iron. These fractures provided suitable mass transfer channels for the inward transfer of water/oxygen molecules to the iron core and the subsequent in situ generation of Fe(II) for the reduction of Cr(VI) to Cr(III). More importantly, systematic characterizations confirmed the generation of an Fe(III)/Cr(III)/Cr(VI) composite on the surface of zero-valent iron during the removal, suggesting its environmental benignancy. This study provides a novel physical zero-valent iron activation method, sheds light on the importance of the iron oxide shell of zero-valent iron on Cr(VI) removal, and clarifies the intrinsic Cr(VI) removal mechanism of zero-valent iron.

Rapid Aerobic Inactivation and Facile Removal of Escherichia coli with Amorphous Zero-Valent Iron Microspheres: Indispensable Roles of Reactive Oxygen Species and Iron Corrosion Products.

Zero valent iron (ZVI) is recently regarded as a promising alternative for water disinfection, but still suffers from low efficiency. Herein we demonstrate that amorphous zerovalent iron microspheres (A-mZVI) exhibit both higher inactivation rate and physical removal efficiency for the disinfection of Escherichia coli than conventional crystalline nanoscale ZVI (C-nZVI) under aerobic condition. The enhanced E. coli inactivation performance of A-mZVI was mainly attributed to more reactive oxygen species (ROSs), especially free •OH, generated by the accelerated iron dissolution and molecular oxygen activation in bulk solution. In contrast, C-nZVI preferred to produce surface bound •OH, and its bactericidal ability was thus hampered by the limited physical contact between C-nZVI and E. coli. More importantly, hydrolysis of dissolved iron released from A-mZVI produced plenty of loose FeOOH to wrap E. coli, increasing the dysfunction of E. coli membrane. Meanwhile, this hydrolysis process lowered the stability of E. coli colloid and caused its rapid coagulation and sedimentation, favoring its physical removal. These findings clarify the indispensable roles of ROSs and iron corrosion products during the ZVI disinfection, and also provide a promising disinfection material for water treatment.

Oxygen Vacancy-Mediated Photocatalysis of BiOCl: Reactivity, Selectivity, and Perspectives.

Semiconductor photocatalysis is a trustworthy approach to harvest clean solar light for energy conversions, while state-of-the-art catalytic efficiencies are unsatisfactory because of the finite light response and/or recombination of robust charge carriers. Along with the development of modern material characterization techniques and electronic-structure computations, oxygen vacancies (OVs) on the surface of real photocatalysts, even in infinitesimal concentration, are found to play a more decisive role in determining the kinetics, energetics, and mechanisms of photocatalytic reactions. This Review endeavors to clarify the inherent functionality of OVs in photocatalysis at the surface molecular level using 2D BiOCl as the platform. Structure sensitivity of OVs on reactivity and selectivity of photocatalytic reactions is intensely discussed via confining OVs onto prototypical BiOCl surfaces of different structures. The critical understanding of OVs chemistry can help consolidate and advance the fundamental theories of photocatalysis, and also offer new perspectives and guidelines for the rational design of catalysts with satisfactory performance.

Hydroxylamine Promoted Goethite Surface Fenton Degradation of Organic Pollutants.

In this study, we construct a surface Fenton system with hydroxylamine (NH2OH), goethite (α-FeOOH), and H2O2 (α-FeOOH-HA/H2O2) to degrade various organic pollutants including dyes (methyl orange, methylene blue, and rhodamine B), pesticides (pentachlorophenol, alachlor, and atrazine), and antibiotics (tetracycline, chloramphenicol, and lincomycin) at pH 5.0. In this surface Fenton system, the presence of NH2OH could greatly promote the H2O2 decomposition on the α-FeOOH surface to produce ·OH without releasing any detectable iron ions during the alachlor degradation, which was different from some previously reported heterogeneous Fenton counterparts. Moreover, the ·OH generation rate constant of this surface Fenton system was 102-104 times those of previous heterogeneous Fenton processes. The interaction between α-FeOOH and NH2OH was investigated with using attenuated total reflectance Fourier transform infrared spectroscopy and density functional theory calculations. The effective degradation of organic pollutants in this surface Fenton system was ascribed to the efficient Fe(III)/Fe(II) cycle on the α-FeOOH surface promoted by NH2OH, which was confirmed by X-ray photoelectron spectroscopy analysis. The degradation intermediates and mineralization of alachlor in this surface Fenton system were then systematically investigated using total organic carbon and ion chromatography, liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry. This study offers a new strategy to degrade organic pollutants and also sheds light on the environmental effects of goethite.

Ball-milled zero-valent iron with formic acid for effectively removing Cu(II)-EDTA accomplished by EDTA ligands oxidative degradation and Cu(II) removal.

Heavy metal complexes in industrial wastewater are challenging to be removed by conventional methods arising from their stable chelating structure. In this study, zero-valent iron (ZVI) was ball-milled with tiny formic acid (FA), and the as-prepared sample (FA-ZVIbm) was attempted to eliminate a model heavy metal complex of Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA to ball-milling could dramatically enhance the performance of ball-milled ZVI (ZVIbm) towards Cu(II)-EDTA removal and increase the removal rate constant by 80 times. This conspicuous improvement of Cu(II)-EDTA elimination was attributed to the ferrous formate (Fe(HCOO)2) shell formed on the surface of FA-ZVIbm. Results revealed that the Fe(HCOO)2 shell facilitated the activation of O2 to reactive oxygen species (ROS) and the leaching of Fe3+. Cu(II)-EDTA was decomplexed through both oxidative destruction and Fe3+ replacement, and the released Cu2+ was reduced by FA-ZVIbm and immobilized synchronously. Meanwhile, the ligands underwent oxidative degradation by ROS, thus avoiding the re-chelation ecological risk. Impressively, FA-ZVIbm could achieve cyclic treatment of actual copper complex wastewater and possessed promising advantage in treatment cost. This study would offer a promising approach for eliminating Cu(II)-EDTA through EDTA ligands degradation and synchronous Cu(II) removal, moreover to shed light on the decomplexation mechanism.

Preparation and characterization of CuInS2 nanocrystals for photovoltaic materials.

Copper indium disulphide (CIS) nanocrystals (NCs) were prepared using a one-pot synthesis. The stoichiometry was optimized based on its current density as measured by photoelectrochemical (PEC) experiments at interfaces between NC films deposited on ITO and 0.1 M methyl viologen dichloride (MV(2+)) solution. This method also offers insight into the kinetics of the photoreaction. A copper poor sulphur rich starting ratio was found to produce a copper-rich, indium-poor and slightly sulphur rich material. Further NC characterization was performed with SEM and TEM to investigate the morphology and crystallinity of the 30-70 nm NCs. The oxidation states of the individual elements were determined to be I, III, and 2- for Cu, In and S, respectively. Characteristics of optimal as-prepared NCs were found to be compatible among high functioning absorbing layers.

Surface oxygen vacancy-dependent molecular oxygen activation for propane combustion over α-MnO2.

Oxygen vacancies (OV), as the sites of molecular oxygen adsorption and activation, play an important role in the catalytic combustion process of volatile organic compounds (VOCs). Revealing the relationship between OV concentration and molecular oxygen activation behavior is of significance to construct the efficient catalysts. Herein, α-MnO2 with different OV concentrations was prepared to investigate the molecular oxygen activation for C3H8 combustion. It is disclosed that the enhanced OV concentration in α-MnO2 induced the reconfiguration of surface metal atoms, resulting in the transformation of oxygen activation configuration from end-on mode to side-on mode. Oxygen molecules in side-on mode possessed more localized electron density and weaker coordination bond strength with surrounding Mn atoms, which were more favorable to adsorb C3H8 molecules and activate C-H bond for the improved combustion performance. This work provides a new understanding to reveal that the increased OV concentration contributes to more efficient VOCs combustion.

Electrochemical removal of gaseous benzene using a flow-through reactor with efficient and ultra-stable titanium suboxide/titanium-foam anode at ambient temperature.

Catalytic oxidation technology is currently considered as a feasible approach to degrade and mineralize volatile organic compounds (VOCs). However, it is still challenging to realize efficient removal of VOCs through catalytic oxidation at room temperature. In our study, a novel flow-through electrocatalytic reactor was designed, composed of porous solid-electrolyte, gas-permeable titanium sub-oxides/titanium-foam (TiSO/Ti-foam) as anode and platinum coated titanium foam (Pt/Ti-foam) as cathode. This device could oxidize nearly 100% of benzene (10 ppm) to carbon dioxide at a current density of 1.2 mA/cm2 under room temperature. More importantly, the device maintained excellent stability over 1000 h. Mechanism of benzene mineralization was discussed. Hydroxyl radicals generated on the TiSO/Ti-foam anode played a crucial role in the oxidation of benzene. This study provides a promising prototype of the electrochemical air purifier, and may find its application in domestic and industrial air pollution control.

Renewable energy driven electroreduction nitrate to ammonia and in-situ ammonia recovery via a flow-through coupled device.

Green ammonia production from wastewater via electrochemical nitrate reduction contributes substantially to the realization of carbon neutrality. Nonetheless, the current electrochemical technology is largely limited by the lack of suitable device for efficient and continuous electroreduction nitrate into ammonia and in-situ ammonia recovery. Here, we report a flow-through coupled device composed of a compact electrocatalytic cell for efficient nitrate reduction and a unit to separate the produced ammonia without any pH adjustment and additional energy-input from the circulating nitrate-containing wastewater. Using an efficient and selective Cl-modified Cu foam electrode, nearly 100% NO3- electroreduction efficiency and over 82.5% NH3 Faradaic efficiency was realized for a wide range of nitrate-containing wastewater from 50 to 200 mg NO3--N L-1. Moreover, this flow-through coupled device can continuingly operate at a large current of 800 mA over 100 h with a sustained NH3 yield rate of 420 µg h-1 cm-2 for nitrate-containing wastewater treatment (50 mg NO3--N L-1). When driven by solar energy, the flow-through coupled device can also exhibit exceptional real wastewater treatment performance, delivering great potential for practical application. This work paves a new avenue for clean energy production and environmental sustainability as well as carbon neutrality.

Oxalated zero valent iron enables highly efficient heterogeneous Fenton reaction by self-adapting pH and accelerating proton cycle.

Heterogeneous Fenton reactions of zero-valent iron (ZVI) requires the sufficient release of Fe(II) to catalyze the H2O2 decomposition. However, the rate-limiting step of proton transfer through the passivation layer of ZVI restricted the Fe(II) release via Fe0 core corrosion. Herein we modified the shell of ZVI with highly proton-conductive FeC2O4·2H2O by ball-milling (OA-ZVIbm), and demonstrated its high heterogeneous Fenton performance of thiamphenicol (TAP) removal, with 500 times enhancement of the rate constant. More importantly, the OA-ZVIbm/H2O2 showed little attenuation of the Fenton activity during 13 successive cycles, and was applicable across a wide pH range of 3.5-9.5. Interestingly, the OA-ZVIbm/H2O2 reaction showed pH self-adapting ability, which initially reduced and then sustained the solution pH in the range of 3.5-5.2. The abundant intrinsic surface Fe(II) of OA-ZVIbm (45.54% vs. 27.52% in ZVIbm, according to Fe 2p XPS profiles) was oxidized by H2O2 and hydrolyzed to generate protons, and the FeC2O4·2H2O shell favored the fast transfer of protons to inner Fe0, therefore, the consumption-regeneration cycle of protons were accelerated to drove the production of Fe(II) for Fenton reactions, demonstrated by the more prominent H2 evolution and nearly 100% H2O2 decomposition by OA-ZVIbm. Furthermore, the FeC2O4·2H2O shell was stable and slightly decreased from 1.9% to 1.7% after the Fenton reaction. This study clarified the significance of proton transfer on the reactivity of ZVI, and provided an efficient strategy to achieve the highly efficient and robust heterogeneous Fenton reaction of ZVI for pollution control.

Microwave-induced formation of platinum nanostructured networks with superior electrochemical activity and stability.

Platinum nanostructured networks (PNNs) can be synthesized through the chemical reduction of H(2)PtCl(6) by benzyl alcohol under microwave irradiation without the introduction of any surfactants, templates, or seeds. The synthesis route utilizes benzyl alcohol as both the reductant and the structure-directing agent, and thus, the process is particularly simple and highly repeatable. The formation of the PNN structure was ascribed to the collision-induced fusion of Pt nanocrystals owing to the cooperative functions of microwave irradiation and benzyl alcohol. Compared with a commercial Pt/C catalyst, the as-prepared PNNs possessed superior electrochemical activity and stability on the oxidation of methanol because of the unique 3D nanostructured networks and abundant defects formed during the assembly process. This study may provide a facile microwave-induced approach for the synthesis of other 3D nanostructured noble metals or their alloys.

Direct growth of tellurium nanorod arrays on Pt/FTO/glass through a surfactant-assisted chemical reduction.

Uniform tellurium nanorod arrays (TNA) have been successfully deposited directly on Pt/FTO (F-doped SnO(2))/glass substrate through a facile surfactant-assisted approach, which involved chemical reduction of TeO(3)(2-) ions by hydrazine hydrate. The whole synthesis process is highly repeatable and performed simply by immersing the Pt/FTO/glass in the solution for a certain time. During the growth of TNA, Pt catalyzed the reduction of TeO(3)(2-) ions by hydrazine hydrate and Te nanoparticles were deposited firmly on the substrate at first. Then, under the regulation of the surfactant (cetyltrimethylammonium bromide, CTAB), the deposited Te grew into nanorod arrays and adhered firmly to the substrate. Similar Te nanorod arrays could also grow on a Pd substrate which has the same catalytic performance as that of Pt. The as-synthesized TNA could be used as a good template to synthesize platinum-and gold-coated nanorods through convenient galvanic replacement. As a demonstration of potential application, the gold/tellurium nanorods showed uniform surface-enhanced Raman scattering (SERS) using rhodamine 6G (Rh6G) as the analyte. This approach provides a simple route for the growth of standing Te nanorods on a substrate, which may be used for the synthesis of other standing one-dimensional materials through a similar mechanism.

Mn2+ promoted Cr(VI) reduction with oxalic acid: The indispensable role of In-situ generated Mn3.

In this study, we demonstrate that Mn2+ can greatly promote the Cr(VI) reduction by oxalic acid at pH<5 via an induction period and a subsequent auto-acceleration process. The Cr(VI) reduction rate constant during the late auto-acceleration process was about 10 times that of the initial induction period. Characterization results revealed that this interesting two-step Cr(VI) reduction phenomenon was attributed to the in-situ generated Mn3+ by the oxidation of Mn2+ with Cr(VI) in the presence of oxalic acid during the induction period. The in-situ generated Mn3+ might complex with oxalate and Cr(VI) to produce a ternary complex, thus facilitating the electron transfer from oxalate to Cr(VI) to automatically accelerate the Cr(VI) reduction process. These findings shed insight into the possible roles of widely existed Mn ions (Mn2+ and Mn3+) and oxalic acid in the transformation of Cr(VI) in natural aquatic environment, and also provided an efficient way to remediate Cr(VI)-containing acid wastewater.

Ascorbate-Promoted Surface Iron Cycle for Efficient Heterogeneous Fenton Alachlor Degradation with Hematite Nanocrystals.

This study reports the H2O2 activation with different hematite nanocrystals and ascorbate ions for the herbicide alachlor degradation at pH 5. We found that hematite nanoplates (HNPs) exposed with {001} facets exhibited better catalytic performance than hematite nanocubes (HNCs) exposed with {012} facets, which was attributed to the formation of inner-sphere iron-ascorbate complexes on the hematite facets. The 3-fold undercoordination Fe cations of {001} facet favors the formation of inner-sphere iron-ascorbate complexes, while the 5-fold undercoordination Fe cations of {012} facet has stereo-hindrance effect, disfavoring the complex formation. The surface area normalized alachlor degradation rate constant (23.3 × 10-4 min-1 L m-2) of HNPs-ascorbate Fenton system was about 2.6 times that (9.1 × 10-4 min-1 L m-2) of HNCs-ascorbate counterpart. Meanwhile, the 89.0% of dechlorination and 30.0% of denitrification in the HNPs-ascorbate Fenton system were also significantly higher than those (60.9% and 13.1%) of the HNCs-ascorbate one. More importantly, the reductive dissolution of hematite by ascorbate was strongly coupled with the subsequent H2O2 decomposition by surface bound ferrous ions through surface iron cycle on the hematite facets in the hematite-ascorbate Fenton systems. This coupling could significantly inhibit the conversion of surface bound ferrous ions to dissolved ones, and thus account for the stability of hematite nanocrystals. This work sheds light on the internal relationship between iron geochemical cycling and contaminants degradation, and also inspires us to utilize surface iron cycle of widely existent hematite for environmental remediation.

One-pot synthesis of spring-like superstructures consisting of layered tin(IV) hydrogen phosphate nanodisks.

Spring-like superstructures consisting of layered tin(IV) hydrogen phosphate nanodisks can be obtained via a one-pot solvothermal reaction of tin tetrachloride and phosphoric acid in ethanol. These superstructures are active anode materials for the lithium-ion battery.

Potassium iodate assisted synthesis of titanium dioxide nanoparticles with superior water-dispersibility.

In this paper, we report a novel polyol process to synthesize highly water-dispersible anatase titanium dioxide (TiO2) nanoparticles (∼5 nm) by the introduction of inorganic oxidizing agent--KIO3. The obtained TiO2 nanoparticles are well dispersible in water at pH≥5.0 and the resulting aqueous dispersion remains stable over months. The superior water-dispersibility of as-formed TiO2 is ascribed to the electrostatic repulsion from carboxylic acid group modified on TiO2 nanoparticles, which is the oxidation product of solvent diethylene glycol (DEG) by KIO3. Based on the characterization results, the formation processes of water-dispersibility TiO2 nanoparticles are proposed. Meanwhile, the synthesized TiO2 nanoparticles are found to be doped by iodine and exhibit excellent photocatalytic activity on degradation of rhodamine-B (RhB) under visible-light irradiation. The further tests demonstrate that the O(2-) is the main active species during photodegradation of RhB.