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In this work, it is proposed an environmental friendly sonophotocatalytic approach to efficiently treat polluted waters from industrial dyes exploiting ZnO micro- and nano-materials. ...For the first time, we deeply investigated the generation of reactive oxygen species (ROS) under ultrasound stimulation of different ZnO structures by Electron Paramagnetic Resonance Spectroscopy (EPR). Indeed, five zinc oxide (ZnO) micro- and nano-structures, i.e. Desert Roses (DRs), Multipods (MPs), Microwires (MWs), Nanoparticles (NPs) and Nanowires (NWs), were studied for the Rhodamine B (RhB) sonodegradation under ultrasonic irradiation. The DRs microparticles demonstrated the best sonocatalytic performance (100% degradation of RhB in 180 min) and the highest OH radicals generation under ultrasonic irradiation. Strikingly, the coupling of ultrasound and sun-light irradiation in a sonophotodegradation approach led to 100% degradation efficiency, i.e. color reduction, of RhB in just 10 min, revealing a great positive synergy between the photocatalytic and sonocatalytic mechanisms. The RhB sonophotocatalytic degradation was also evaluated at different initial dye concentrations and with the presence of anions in solution. It was demonstrated a good stability over repeated cycles of dye treatment, which probe the applicability of this technique with industrial effluents. In conclusion, sonophotocatalytic degradation synergizing sunlight and ultrasound in the presence of DRs microparticles shows a great potential and a starting point to investigate further the efficient treatment of organic dyes in wastewater.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The development of efficient and robust earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) is an ongoing challenge. Here, a novel and stable trimetallic NiFeCr layered double ...hydroxide (LDH) electrocatalyst for improving OER kinetics is rationally designed and synthesized. Electrochemical testing of a series of trimetallic NiFeCr LDH materials at similar catalyst loading and electrochemical surface area shows that the molar ratio Ni:Fe:Cr = 6:2:1 exhibits the best intrinsic OER catalytic activity compared to other NiFeCr LDH compositions. Furthermore, these nanostructures are directly grown on conductive carbon paper for a high surface area 3D electrode that can achieve a catalytic current density of 25 mA cm−2 at an overpotential as low as 225 mV and a small Tafel slope of 69 mV dec−1 in alkaline electrolyte. The optimized NiFeCr catalyst is stable under OER conditions and X‐ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and elemental analysis confirm the stability of trimetallic NiFeCr LDH after electrochemical testing. Due to the synergistic interactions among the metal centers, trimetallic NiFeCr LDH is significantly more active than NiFe LDH and among the most active OER catalysts to date. This work also presents general strategies to design more efficient metal oxide/hydroxide OER electrocatalysts.
NiFe‐layered double hydroxides (LDHs) and oxyhydroxides have been the benchmark electrocatalysts toward oxygen evolution reaction. When a third and multivalent Cr metal ion is rationally added to the modular LDH structures, the highest intrinsic catalytic activity and performance are achieved with earth‐abundant trimetallic NiFeCr LDH electrocatalysts.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Oxygen vacancy plays an important role in many fields, such as photocatalysis, energy storages, electro-catalysis, which has been widely investigated both by experiment and theoretical calculations. ...Herein, this review presents the new type and advanced methods to detect the existence of oxygen vacancies in nanomaterials, such as, electron paramagnetic resonance, synchrotron radiation-based X-ray absorption fine structure, X-ray photoelectron spectroscopy and positron annihilation spectroscopy measurements. In addition, we provide some perspectives on the challenge and new direction for future research in oxygen vacancy. We hope that this minireview can offer some useful contributions to the future development of defective nanomaterials for diverse application.
•Recent progress on the development of oxygen vacancies.•The methods of detecting oxygen vacancies were summarized.•The current challenges and opportunities for the detection of oxygen vacancies were discussed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Fenton reaction was used to produce hydroxyl radicals under conditions similar to AOPs with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap agent in electron paramagnetic resonance (EPR) ...analysis. A theoretical kinetics model was developed to determine conditions under which the spin-adduct DMPO-OH is not further oxidized by Fe3+ and excessive radicals, so that hydroxyl radicals concentration could be accurately inferred. Experiments were designed based upon the model and H2O2 and Fe2+ concentrations were varied from 1 to 100 mM and from 0.1 to 10 mM, respectively, with a constant H2O2: Fe2+ ratio of 10:1. Results confirmed that DMPO concentration should be at least 20 times higher than the concentration of H2O2 and 200 times higher than iron concentration to produce stable DMPO-OH EPR signal. When DMPO: H2O2 ratio varied from 1 to 10, DMPO-OH could generate intermediates and be further oxidized leading to the apparition of an additional triplet. This signal was attributed to a paramagnetic dimer: its structure and a formation mechanism were proposed. Finally, the utilization of sodium sulfite and catalase to terminate Fenton reaction was discussed. Catalase appeared to be compatible with DMPO. However, sodium sulfite should be avoided since it reacted with DMPO-OH to form DMPO-SO3.
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•Concentrations in Fenton reagent similar to AOPs/EAOPs were used.•A theoretical model was developed and experiments were based on this model.•DMPO should be respectively 20 and 200 times higher than H2O2 and Fe2+.•When Fenton reagent is in excess, DMPO-OH is degraded into a paramagnetic dimer.•Utilization of catalase as a H2O2 quencher is compatible with DMPO as a spin trap.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Abstract
Construction of Z-scheme heterostructure is of great significance for realizing efficient photocatalytic water splitting. However, the conscious modulation of Z-scheme charge transfer is ...still a great challenge. Herein, interfacial Mo-S bond and internal electric field modulated Z-scheme heterostructure composed by sulfur vacancies-rich ZnIn
2
S
4
and MoSe
2
was rationally fabricated for efficient photocatalytic hydrogen evolution. Systematic investigations reveal that Mo-S bond and internal electric field induce the Z-scheme charge transfer mechanism as confirmed by the surface photovoltage spectra, DMPO spin-trapping electron paramagnetic resonance spectra and density functional theory calculations. Under the intense synergy among the Mo-S bond, internal electric field and S-vacancies, the optimized photocatalyst exhibits high hydrogen evolution rate of 63.21 mmol∙g
−1
·h
−1
with an apparent quantum yield of 76.48% at 420 nm monochromatic light, which is about 18.8-fold of the pristine ZIS. This work affords a useful inspiration on consciously modulating Z-scheme charge transfer by atomic-level interface control and internal electric field to signally promote the photocatalytic performance.
•A systematic EPR method to accurately identify radicals in UV-AOPs was presented.•EPR method on identification of SO4·− without the interference of ·OH was proposed.•Alkoxy and alkyl radicals ...produced in UV/peracetic acid system were identified.•Iodine-related radicals and hydrated electron in UV/IO4− system were identified.•Key characteristics on various DMPO-radical adducts in EPR spectrum were summarized.
Accurate identification of radicals in advanced oxidation processes (AOPs) is important to study the mechanisms on radical production and subsequent oxidation-reduction reaction. The commonly applied radical quenching experiments cannot provide direct evidences on generation and evolution of radicals in AOPs, while electron paramagnetic resonance (EPR) is a cutting-edge technology to identify radicals based on spectral characteristics. However, the complexity of EPR spectrum brings uncertainty and inconsistency to radical identification and mechanism clarification. This work presented a comprehensive study on identification of radicals by in-situ EPR analysis in four typical UV-based homogenous AOPs, including UV/H2O2, UV/peroxodisulfate (and peroxymonosulfate), UV/peracetic acid and UV/IO4− systems. Radical formation mechanism was also clarified based on EPR results. A reliable EPR method using organic solvents was proposed to identify alkoxy and alkyl radicals (CH3C(=O)OO·, CH3C(=O)O· and ·CH3) in UV/PAA system. Two activation pathways for radical production were proposed in UV/IO4− system, in which the produced IO3·, IO4·, ·OH and hydrated electron were precisely detected. It is interesting that addition of specific organic solvents can effectively identify oxygen-center and carbon-center radicals. A key parameter in EPR spectrum for 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin adduct, AH, is ranked as: ·CH3 (23 G) >·OH (15 G) >IO3· (12.9 G) >O2·− (11 G) ≥·OOH (9–11 G) ≥IO4· (9–10 G) ≥SO4·− (9–10 G) >CH3C(=O)OO· (8.5 G) > CH3C(=O)O· (7.5 G). This study will give a systematic method on identification of radicals in AOPs, and shed light on the insightful understanding of radical production mechanism.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Electron spins permeate every aspect of science and influence numerous chemical processes: they underpin transition metal chemistry and biochemistry, mediate photosynthesis and photovoltaics and are ...paramount in the field of quantum information, to name but a few. Electron paramagnetic resonance (EPR) spectroscopy detects unpaired electrons and provides detailed information on structure and bonding of paramagnetic species. In this tutorial review, aimed at non-specialists, we provide a theoretical framework and examples to illustrate the vast scope of the technique in chemical research. Case studies were chosen to exemplify systematically the different interactions that characterize a paramagnetic centre and to illustrate how EPR spectroscopy may be used to derive chemical information.
This tutorial review provides a basic theoretical background and illustrates the chemical questions that may be answered using EPR spectroscopy through a representative range of examples.
The Mn2 complex MnII2(TPDP)(O2CPh)2(BPh4) (1, TPDP = 1,3-bis(bis(pyridin-2-ylmethyl)amino)propan-2-ol, Ph =phenyl) was prepared and subsequently characterized via single-crystal X-ray diffraction, ...X-ray absorption, electronic absorption, and infrared spectroscopies, and mass spectrometry. 1 was prepared in order to explore its properties as a structural and functional mimic of class Ib ribonucleotide reductases (RNRs). 1 reacted with superoxide anion (O2•–) to generate a peroxido-MnIIMnIII complex, 2. The electronic absorption and electron paramagnetic resonance (EPR) spectra of 2 were similar to previously published peroxido-MnIIMnIII species. Furthermore, X-ray near edge absorption structure (XANES) studies indicated the conversion of a MnII2 core in 1 to a MnIIMnIII state in 2. Treatment of 2 with para-toluenesulfonic acid (p-TsOH) resulted in the conversion to a new MnIIMnIII species, 3, rather than causing O—O bond scission, as previously encountered. 3 was characterized using electronic absorption, EPR, and X-ray absorption spectroscopies. Unlike other reported peroxido-MnIIMnIII species, 3 was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib RNRs, however without accessing the MnIIIMnIV state.
Unlike other reported MnIIMnIII species, the current example was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib ribonucleotide reductases, however without accessing the MnIIIMnIV state. Display omitted
•MnII2(TPDP)(O2CPh)2(BPh4) (1) was prepared in order to explore its properties as a structural and functional mimic of class Ib ribonucleotide reductases (RNRs).•1 reacted with superoxide anion (O2•–) to generate a peroxido-MnIIMnIII complex, 2.•Treatment of 2 with para-toluenesulfonic acid (p-TsOH) resulted in the conversion to a new MnIIMnIII species, 3, rather than causing O—O bond scission.•Unlike other reported MnIIMnIII species, 3 was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib RNRs, however without accessing the MnIIIMnIV state.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The tailorable structure and electronic structure of metal–organic frameworks (MOFs) greatly facilitate their modulated light harvesting, redox power, and consequently photocatalysis. Herein, a ...representative MOF, UiO-66, was furnished by installing Fe3+ onto the Zr-oxo clusters, to give Fe-UiO-66, which features extended visible light harvesting, based on metal-to-cluster charge transfer (MCCT). The Fe-UiO-66 with unique electronic structure and strong oxidizing power exhibits visible light-driven water oxidation, which is impossible for pristine UiO-66. More strikingly, under visible irradiation, the generated holes over Fe-UiO-66 are able to exclusively convert H2O to hydroxide radicals, initiating and driving the activation of stubborn C-H bond, such as toluene oxidation. The electrons reduce O2 to O2 •‑ radicals that further promote the oxidation reaction. The related catalytic mechanism and the structure–activity relationship have been investigated in detail. As far as we know, this is not only an unprecedented report on activating “inert” MOFs for photocatalytic C-H activation but also the first work on extended light harvesting and enhanced photocatalysis for MOFs by introducing an MCCT process.
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