X-ray Adsorption Fine Structure Research Articles

Rubik’s cube PBA frameworks for optimizing the electrochemical performance in alkali metal-ion batteries

PBA frameworks have stood out among metal–organic frameworks because of their easy preparation, excellent stability, porous structures, and rich redox properties. Unfortunately, their non-ideal conductivity and significant volume expansion during cycling prevent more widespread application in alkali-metal-ion (Li+, Na+, and K+) batteries. By changing the type and molar ratio of metal ions, Rubik’s PBA frameworks with infinite structural variations were obtained in this study, just like the Rubik’s cube undergoes infinite changes during the rotation. X-ray adsorption fine structure measurements have documented the existence and determined the coordination environment of the metal ions in the Rubik’s PBA framework. Benefiting from the more stable Rubik’s cube structures with diverse composition, enhanced conductivity, and greater adsorption capacity, the obtained Rubik’s cubes CoM-PBA anodes, especially CoZn-PBA deliver the enhanced cycling and rate performance in all the alkali-metal-ion batteries. The findings are supported by density functional theory calculations. Ex-situ X-ray photoelectron spectroscopy, and in-situ X-ray diffraction measurements were undertaken to explore the storage mechanism of CoZn-PBA anodes. Our results further demonstrate that the Rubik’s cube PBA framework-based materials could be widely applied in the field of alkali-metal-ion batteries.

Oxygen-Bridged Cu Binuclear Sites for Efficient Electrocatalytic CO2 Reduction to Ethanol at Ultralow Overpotential.

Electrocatalytic CO2 reduction (CO2RR) to alcohols offers a promising strategy for converting waste CO2 into valuable fuels/chemicals but usually requires large overpotentials. Herein, we report a catalyst comprising unique oxygen-bridged Cu binuclear sites (CuOCu-N4) with a Cu···Cu distance of 3.0-3.1 Å and concomitant conventional Cu-N4 mononuclear sites on hierarchical nitrogen-doped carbon nanocages (hNCNCs). The catalyst exhibits a state-of-the-art low overpotential of 0.19 V (versus reversible hydrogen electrode) for ethanol and an outstanding ethanol Faradaic efficiency of 56.3% at an ultralow potential of -0.30 V, with high-stable Cu active-site structures during the CO2RR as confirmed by operando X-ray adsorption fine structure characterization. Theoretical simulations reveal that CuOCu-N4 binuclear sites greatly enhance the C-C coupling at low potentials, while Cu-N4 mononuclear sites and the hNCNC support increase the local CO concentration and ethanol production on CuOCu-N4. This study provides a convenient approach to advanced Cu binuclear site catalysts for CO2RR to ethanol with a deep understanding of the mechanism.

Isolated Ni-atom catalyst supported on Ti3C2Tx with an asymmetrical C-Ni-N structure for the hydrogen evolution reaction.

Single-atom catalysts (SACs), distinguished by their exceptional atomic efficiency and modifiable coordination structures, find wide-ranging applicability, notably in the context of the hydrogen evolution reaction (HER). Herein, we synthesized a Ti3C2Tx-based Ni single-atom catalyst (Ni SA@N-Ti3C2Tx) by immersing a single Ni atom into the Ti vacancies of Ti3C2Tx and using a N-doping strategy. X-Ray adsorption fine structure revealed the formation of local Ni-N1C1 and an unsaturated C-Ni-N bridge configuration for isolated Ni species. Moreover, Ni SA@N-Ti3C2Tx exhibited an excellent HER performance with an overpotential of 63 mV at 10 mV cm-2. This work could enable use of MXene-based SACs in the HER.

Regulation of SiO2 Nanoparticles on the Adsorptive Fractionation of Dissolved Organic Matter by Goethite.

SiO2 nanoparticles (SiO2NPs) are most widely available and coexisting with DOM at the mineral-water interface; however, the role of SiO2NPs in DOM fractionation and the underlying mechanisms have not been fully understood. Using Fourier transform ion cyclotron resonance mass spectrometry, combined with Fourier transform infrared spectroscopy and X-ray adsorption fine structure spectroscopy, was employed to investigate the adsorptive fractionation of litter layer-derived DOM on goethite coexisting with SiO2NPs under different pH conditions. Results indicated that the inhibitory effect of the coexisting SiO2NPs on OM sorbed by goethite was waning as environmental pH increased due to the reduced steric interactions and the concurrent elevated hydrogen bonding/hydrophobic partitioning interactions on the goethite surface. We observed the coexisting SiO2NPs inhibited the adsorption of high carboxylic-containing condensed aromatic/aromatics compounds on goethite under different pH conditions while improving the adsorption of highly unsaturated aliphatic/phenolic and carbohydrate-like compounds in an alkaline and/or circumneutral environment. More nitrogen-containing structures may favor the adsorption of phenolic and nonaromatic compounds to goethite by counteracting the negative effect of SiO2NPs. These findings suggest that DOM sequestration may be significantly regulated by the coexisting SiO2NPs at the mineral-water interface, which may further influence the carbon-nitrogen cycling and contaminant fate in natural environments.

Ultrathin NiV Layered Double Hydroxide for Methanol Electrooxidation: Understanding the Proton Detachment Kinetics and Methanol Dehydrogenation Oxidation.

Electrochemical methanol oxidation reaction (MOR) is regarded as a promising pathway to obtain value-added chemicals and drive cathodic H2 production, while the rational design of catalyst and in-depth understanding of the structure-activity relationship remains challenging. Herein, the ultrathin NiV-LDH (u-NiV-LDH) with abundant defects is successfully synthesized, and the defect-enriched structure is finely determined by X-ray adsorption fine structure etc. When applied for MOR, the as-prepared u-NiV-LDH presents a low potential of 1.41V versus RHE at 100mA cm-2, which is much lower than that of bulk NiV-LDH (1.75V vs RHE) at the same current density. The yield of H2 and formate is 98.2% and 88.1% as its initial over five cycles and the ultrathin structure of u-NiV-LDH can be well maintained. Various operando experiments and theoretical calculations prove that the few-layer stacking structure makes u-NiV-LDH free from the interlayer hydrogen diffusion process and the hydrogen can be directly detached from LDH laminate. Moreover, the abundant surface defects upshift the d-band center of u-NiV-LDH and endow a higher local methanol concentration, resulting in an accelerated dehydrogenation kinetics on u-NiV-LDH. The synergy of the proton detachment from the laminate and the methanol dehydrogenation oxidation contributes to the excellent MOR performance of u-NiV-LDH.

Accumulation of Ag(0) Single Atoms at Water/Mineral Interfaces during Sunlight-Induced Reduction of Ionic Ag by Phenolic DOM.

Silver (Ag) undergoes a complex and dynamic Ag+/Ag0 cycle under environmental conditions. The Ag+ → Ag nanoparticles (AgNPs) transformation due to the combined actions of sunlight, O2, and dissolved organic matter has been a well-known environmental phenomenon. In this study, we indicate that this process may be accompanied by a pronounced accumulation of Ag(0) single atoms (Ag-SAs) on the minerals' surfaces. According to spherical aberration-corrected scanning transmission electron microscopy and high-energy-resolution X-ray adsorption fine structure analyses, humic acid (HA) and phenol (PhOH) can induce Ag-SAs accumulation, whereas oxalic acid causes only AgNPs deposition. Ag-SAs account for more than 20 wt % of total Ag(0) on the γ-Al2O3 surfaces during HA- and PhOH-mediated photolysis processes. HA also causes Ag-SAs to accumulate on two other prevalent soil minerals, SiO2 and Fe2O3, and the fractions of Ag-SAs are about 15 wt %. Our mechanism studies suggest that a phenolic molecule acts as a reducing agent of Ag+ and a stabilizer of Ag-SAs, protecting Ag-SAs against autocatalytic nucleation.

Multivariate and multi-interface insights into carbon and energy recovery and conversion characteristics of hydrothermal carbonization of biomass waste from duck farm

High lipid, high nitrogen duck manure (DM) with high lipid, high lignocellulosic litter materials (LM) are the main wet biomass wastes from duck farms and both are naturally abundant carbon resources. The synthesis of duck farming biomass waste into carbon-rich materials for high value utilization by hydrothermal carbonization (HTC), which can directly treat wet biomass, has not been investigated. In this study, the physicochemical properties of hydrochar derived from co-HTC of DM and LM and its carbon and energy recovery patterns were systematically investigated under multivariate conditions of raw materials ratios, solids contents, temperatures and residence times. The application of synchrotron-based near-edge X-ray adsorption fine structure technique (C K-edge NEXAFS) combined with gas chromatography-mass spectrometry (GC–MS) to the hydrochar and hydrothermal liquid, respectively. At multiple interfaces provided an in-depth analysis of the important material transformations of the co-HTC process and the structure of the hydrochar. Extending residence time (180 min) and increasing LM ratio (M@4%) in co-HTC reaction of DM and LM is beneficial to achieve hydrochar containing higher carbon content (44.84%) at lower reaction temperatures (180 °C). The heating value (HHV) of the hydrochar ranges between 17.12 and 25.05 MJ/kg. The carbon recovery rate of the co-HTC of DM and LM all exceeded 55% and was more closely related to the carbon content of the hydrochar than to its yield. Additionally, the model ERR=0.97±0.01CRR+2.40±0.71 (R2 = 0.99, P < 0.01) was developed to predict energy recovery rate (ERR) based on carbon recovery rate (CRR). Esters were an important intermediate during co-HTC of DM and LM, and the derived hydrochar consisted of a wide range of polycyclic aromatic hydrocarbons, alkanes and N-aromatic heterocycles as well as polyfuran, pyrrole and pyridine structures.

Environment-friendly electrochemical mechanical polishing using solid polymer electrolyte/CeO2 composite pad for highly efficient finishing of 4H-SiC (0001) surface

Silicon carbide (SiC) is a promising material for use in high-performance power electronic devices. However, the SiC wafer is costly partly due to difficulties in machining the SiC surface. Furthermore, its prolonged polishing process requires massive amounts of resources, which increases the environmental impact of the wafer production process. Herein, we developed an environment-friendly and highly efficient electrochemical mechanical polishing (ECMP) method for 4H-SiC (0001) that does not require any liquid containing harsh chemicals and uses an ion-conductive composite pad consisting of a solid polymer electrolyte and CeO2 particles. The SiC surface finished using the proposed method was analyzed using X-ray analysis, Raman spectroscopy, atomic force microscopy, and X-ray adsorption fine structure measurements. A high material removal rate (MRR) of approximately 15 µm h−1, which is almost 10 times higher than that obtained by CMP, was achieved by the proposed ECMP method under the current density and mechanical condition of 25 mA cm−2 and 2.3 × 103 kPa min−1, respectively. The proposed method, which can remove surface damage and produce a smooth surface on the entire wafer scale with a high MRR without a liquid electrolyte, should prove to be advantageous for environment-friendly SiC wafer preparation.

Ultrathin Niobate Nanosheet Assembly with Au NPs and CdS QDs as a Highly Efficient Photocatalyst.

Niobate nanosheets have aroused widespread interest in recent years for their prospects in catalysis. The exploration of 2D niobate catalysis with stable and efficient properties is still the focus in chemistry and materials science. Herein, the successful fabrication of 2D CdS/Au/HNb3 O8 catalyst is demonstrated which revealed efficient photocatalytic properties in H2 evolution, oxidative self-coupling of amines to imines, and degradation of dyes. Especially the assembled architecture can give a rate of 5.85 mmol ⋅ g-1 ⋅ h-1 of photocatalytic H2 evolution, an ∼254-fold enhancement, compared with bare HNb3 O8 nanosheets under identical conditions. In accordance with density functional theory (DFT) and X-ray adsorption fine structure (XAFS) analyses, the vast improvements are benefited from efficient migration and separation of charge carriers. Besides, the surface plasma resonance (SPR) effect of Au NPs enhances the light harvesting capacity and boosts the generation of hot electrons, efficiently improving the visible-light absorption.

Construction of Synergistic Co and Cu Diatomic Sites for Enhanced Higher Alcohol Synthesis

Construction of Synergistic Co and Cu Diatomic Sites for Enhanced Higher Alcohol Synthesis

Nitrogen-doped carbon black supported synergistic palladium single atoms and nanoparticles for electrocatalytic oxidation of methanol

For commercially viable direct methanol fuel cells, electrocatalysts play a crucial role in motivating the sluggish methanol oxidation reaction (MOR) over anode. Unfortunately, the large-scale applications of current MOR catalysts are hampered by their poor tolerance to poisoning and fast activity degradation. Herein, a unique composite catalyst comprised of partial Pd nanoparticles and partial Pd single atoms (PdNPs/Pd-Nx@C) is developed. The as-fabricated catalyst exhibits remarkable activity of 9.45 mA·cm−2 towards MOR in alkaline solution, which is 7.05 and 3.92 times that of commercial Pd/C and nanoparticle type (PdNPs@C) electrocatalysts, respectively. Impressively, the PdNPs/Pd-Nx@C shows the highest long-time stability with 90.38% and 89.8% of the initial activity retained after 3600 s chronoamperometry (CA) test and 2000 cycles of cyclic voltammetry (CV) measurements with accelerated durability test (ADT), respectively. Combined with high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM), X-ray adsorption fine structure (XAFS) spectra and X-ray photoelectron spectroscopy (XPS) analyses, the superior performance of PdNPs/Pd-Nx@C can be ascribed to the synergistic effect from the Pd single atoms, N-doped carbon supports and Pd nanoparticles. Notably, the embedded Pd single atoms are liable to transfer electrons to the substrate due to the electronic metal-support interactions (EMSI) and the charge transfer between Pd nanoparticles and carbon supports is suppressed, inducing a weak adsorption strength of poisonous carbonous intermediate species on active Pd nanoparticles and improved poisoning tolerance in MOR process, which is verified by density functional theory (DFT) calculations as well as CO-stripping voltammetry experiments. This work not only contributes the first example of a synergistic catalyst between nanoparticles and single atoms for MOR but also deepens the knowledge on the metal-support interaction.

Biomass derived Fe-N/C catalyst for efficiently catalyzing oxygen reduction reaction in both alkaline and neutral pH conditions

Fe-N/C is a promising oxygen reduction reaction (ORR) catalyst to substitute the current widely used precious metal platinum. Cost-effectively fabricating the Fe-N/C material with high catalytic activity and getting in-depth insight into the responsible catalytic site are of great significance. In this work, we proposed to use biomass, tea leaves waste, as the precursor to prepare ORR catalyst. By adding 5% FeCl3 (wt%) into tea precursor, the pyrolysis product (i.e., 5%Fe-N/C) exhibited an excellent four-electron ORR activity, whose onset potential was only 10 mV lower than that of commercial Pt/C. The limiting current density of 5%Fe-N/C (5.75 mA/cm2) was even higher than Pt/C (5.44 mA/cm2). Compared with other biomass or metal organic frameworks derived catalysts, 5%Fe-N/C showed similar ORR activity. Also, both the methanol tolerance and material stability performances of as-prepared 5%Fe-N/C catalyst were superior to that of Pt/C. X-ray adsorption fine structure characterization revealed that the FeN4O2 might be the possible catalytic site. An appropriate amount of iron chloride addition not only facilitated catalytic site formation, but also enhanced material conductivity and reaction kinetics. The results of this work may be useful for the Fe based transition metal ORR catalyst design and application.

In Situ XAFS, XRD, and DFT Characterization of the Sulfur Adsorption Sites on Cu and Ce Exchanged Y Zeolites

Adsorptive desulfurization with Cu and Ce ion-exchanged Y zeolite (CuCeY) has proven to be an effective method for the removal of sulfur compounds from hydrocarbon fuels. In this study, Cu and Ce exchanged Y materials including CuY, CeY, and CuCeY were prepared and examined to investigate the mechanism behind the superior sulfur adsorption and selectivity of CuCeY. In situ conditions were used to study the materials as prepared for optimal desulfurization. X-ray diffraction (XRD) confirmed the absence of large well-ordered crystalline phases from metallic or oxide Cu and Ce after the reduction of the samples. The oxidation states and local environments of Cu and Ce were determined using X-ray adsorption fine structure (XAFS) analysis and correlated to theoretical findings obtained from density functional theory (DFT) calculations. XAFS data indicate the successful reduction of Cu species to Cu+ and Cu0, and Ce to Ce3+. Analysis of XAFS spectra located Cu and Ce within the Y zeolite framework with Cu cations in the six-member ring sites and as small metallic Cu clusters. Ce cations were found to occupy both six-member ring and hexagonal prism sites. These results reveal the structure of CuCeY as prepared for desulfurization and provide insight into its superior sulfur adsorption performance.

Control of Local Electronic Structure of Pd Single Atom Catalyst by Adsorbate Induction.

Aiming at regulating and controlling the localized electronic states while maintaining the metal atoms in the isolation form, an in situ adsorbate induced strategy is proposed at a programmed temperature to activate Zr-based metal-organic framework (MOF) supported single Pd atom catalyst. It is discovered that in situ treatment environments trigger the change of lattice parameters in MOF materials by reaction heat effect, observed by in situ X-ray diffraction, spherical aberration-corrected electron microscope, and X-ray adsorption fine structure (XAFS). The as-obtained electron-deficient Pd single atoms are critical to the high intrinsic activity (turnover frequency of 0.132 s-1 ) and selectivity of 93% with the long-term stability in the semihydrogenation of acetylene, which can be comparable to the state-of-the-art Pd catalysts. This superior catalytic behavior correlates with the reduced C2 H4 desorption energy and the activation barriers for the hydrogenation, confirmed by density functional theory calculation.

Redox-driven changes in organic C stabilization and Fe mineral transformations in temperate hydromorphic soils

Paddy soils experience long-term redox alternations affecting the interactions between the biogeochemical cycling of iron (Fe) and carbon (C). Differences in particle aggregation and soil organic matter (SOM) turnover are likely to both affect and be affected by the trajectory of Fe mineral evolution/crystallinity with redox fluctuations. We hypothesized that the legacy effects of redox cycling under paddy management affects particle aggregation, the distribution and mineralogy of Fe (hydr)oxides between particle-size fractions, and the interaction with SOM stabilization. Moreover, we expected underlying processes to be different in paddy eluvial and illuvial horizons, particularly due to the different inputs and redox conditions these horizons experience. To test these hypotheses, we evaluated the distribution of Fe species and organic C between different aggregate and particle-size fractions in topsoil (eluvial) and subsoil (illuvial) horizons of soils under long-term paddy and non-paddy management in NW Italy, as well as mineralogical changes in Fe phases by Fe K-edge Extended X-ray Adsorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Our findings indicate that although paddy topsoils are depleted in hydrous Fe oxides with respect to non-paddy soils, they can stabilize important amounts of C through mineral associations, particularly with finer particle-size fractions rich in less crystalline Fe phases. We also show that redox cycling can influence microaggregate stability and consequently the distribution of Fe phases and OC between intra and inter-microaggregate fractions. On the other hand, illuvial horizons under paddy management were enriched in short-range ordered hydrous Fe oxides and this contributed to enhanced microaggregate formation and C stabilization with respect to non-paddy subsoils.

Metastable Facet-Controlled Cu2WS4 Single Crystals with Enhanced Adsorption Activity for Gaseous Elemental Mercury.

Purposively designing environmental advanced materials and elucidating the underlying reactivity mechanism at the atomic level allows for the further optimization of the removal performance for contaminants. Herein, using well facet-controlled I-Cu2WS4 single crystals as a model transition metal chalcogenide sorbent, we investigated the adsorption performance of the exposed facets toward gaseous elemental mercury (Hg0). We discovered that the decahedron exhibited not only facet-dependent adsorption properties for Hg0 but also recrystallization along the preferential [001] growth direction from a metastable state to the steady state. Besides, the metastable crystals with a predominant exposure of {101} facets dominated the promising adsorption efficiency (about 99% at 75 °C) while the saturated adsorption capacity was evaluated to be 2.35 mg·g-1. Subsequently, comprehensive characterizations and X-ray adsorption fine structure (XAFS), accompanied by density functional theory (DFT) calculations, revealed that it might be owing to the coordinatively unsaturated local environment of W atoms with S defects and the surface relative stability of different facets, which could be affected by the change in surface atom configuration. Hence, the new insight into the facet-dependent adsorption property of transition metal chalcogenide for Hg0 may have important implications, and the atomic-level study directly provides instructions for development and design of highly efficient functional materials.

(Invited) Structural Analysis of Rust Layer Formed on Carbon Steel Exposed to Atmospheric Corrosion Environments Using Synchrotron Radiation X-Rays

Carbon steel has been a beneficial material to humankind, but unfortunately is easily oxidized back to iron ore if the steel touches with an atmospheric environment. This phenomenon is well-known as atmospheric corrosion which proceeds under an electrolyte film containing oxygen and water covering the steel surface. Through atmospheric corrosion, surface of a carbon steel becomes covered with rust layer which largely affects the corrosion process of the steel. In this study, structure of rust layer formed on carbon steel exposed to atmospheric environment is explored using synchrotron radiation X-rays.The X-ray diffraction (XRD) and X-ray adsorption fine structure (XAFS) analyses for the rust layer containing Cr revealed that Cr is incorporated in the corrosion product with goethite (alpha-FeOOH) structure and resultantly the particle size of which becomes less than ten nanometer. This ultrafine Cr-goethite 1) works as a strong protective barrier for the corrosives in the atmosphere. XAFS spectra at Cr K-edge explain the probable site of Cr3+ in goethite and this Cr3+ gives cation selectivity to goethite in the following way. It was shown by the extended X-ray absorption fine structure analysis that the incorporated Cr3+ is not located at a definite distance from Fe3+ and is coordinated with O2-; therefore Cr3+ forms CrOx 3-2x complex ion having negative charge. Namely, CrOx 3-2x complex ion is adsorbed to the goethite crystal surface and its negative charge gives cation selectivity which reduces penetration of corrosive anion such as Cl- through the rust layer.In-situ XRD observation of the formation process of rust layer directly indicates the Fe2+ - Fe3+ change during the corrosion processes of a carbon steel. An addition of metallic salt to the electrolyte film covering the steel surface changes the rust formation process. For instance, Cl- promotes the formation of akaganeite (beta-FeOOH) and some other metallic salts help goethite formation 2).The addition of nickel sulfate to the surface of carbon steel in the chloride and sulfuric acid mist environment promoted the formation of goethite and akaganeite 3). It was assumed that this akaganeite was not conventional β-FeOOH with a tetragonal crystal structure, but monoclinic akaganeite containing Ni2+. This monoclinic akaganeite might reduce the corrosion rate of the carbon steel since the monoclinic akaganeite incorporates corrosive Cl- in the crystal structure of the akaganeite.Based on the arguments mentioned above, it is said that the rust structure is greatly affected by the coexisting ions on the steel surface and resultantly controls corrosion process of a carbon steel.References1) M. Yamashita, H. Konishi, J. Mizuki and H. Uchida, Materials Transactions, 45, No.6, 1920-1924(2004).2) M. Yamashita, H. Konishi, T. Kozakura, J. Mizuki and H. Uchida, Materials Transactions, 46, No.5, 1004-1009 (2005).3) S. Hayashida, M. Takahashi, H. Deguchi, H. Tsuchiya, K. Hanaki, M. Yamashita and S. Fujimoto, Zairyo-to-Kankyo, 69, No.5, 148-153(2020).

Co-Induced Electronic Optimization of Hierarchical NiFe LDH for Oxygen Evolution.

Developing efficient and stable non-noble electrocatalysts for the oxygen evolution reaction (OER) remains challenging for practical applications. While nickel-iron layered double hydroxides (NiFe-LDH) are emerging as prominent candidates with promising OER activity, their catalytic performance is still restricted by the limited active sites, poor conductivity and durability. Herein, hierarchical nickel-iron-cobalt LDH nanosheets/carbon fibers (NiFeCo-LDH/CF) are synthesized through solvent-thermal treatment of ZIF-67/CF. Extended X-ray adsorption fine structure analyses reveal that the Co substitution can stabilize the Fe local coordination environment and facilitate the π-symmetry bonding orbital in NiFeCo-LDH/CF, thus modifying the electronic structures. Coupling with the structural advantages, including the largely exposed active surface sites and facilitated charge transfer pathway ensured by CF, the resultant NiFeCo-LDH/CF exhibits excellent OER activity with an overpotential of 249mV at 10mA cm-1 as well as robust stability over 20 h.

Improvement of crystallization in CVD diamond coating induced by femtosecond laser irradiation

Herein, structural modification of a chemical vapor deposit (CVD) diamond film by a low fluence femtosecond laser irradiation has been studied with Raman spectroscopy, X-ray adsorption fine structure (XAFS) spectroscopy, and X-ray diffraction (XRD). Polycrystalline CVD diamond films of approximately 20 μm thickness were irradiated with femtosecond laser of varied defocus distances corresponding to the laser fluence range of 0.1–127.3 J/cm2. At fluences below 1.27 J/cm2, although there was no observable change in the appearance of the film surface, however, the FWHM of the diamond peak in the Raman spectra was observed to reduce considerably from 17 to 7 cm−1. Furthermore, the higher fraction of diamond phase with the increase in laser fluence strongly suggests that the microstructure of the diamond film has been modified by the femtosecond laser. By employing XAFS measurement, it can be found that after irradiation, the weak π* fine structure in the pre-edge almost vanished in response to the significant increase in σ* adsorption; further, a distinct diamond crystal characteristic peak was observed, which further confirms the femtosecond laser-induced modification, and its occurrence inside the bulk film. XRD results also pointed out that the improved diamond crystallinity with the integral intensities increased by approximately 20% after the femtosecond irradiation. Based on the above-mentioned results, an improvement in the crystallinity of CVD diamond under the low-fluence femtosecond laser irradiation has been confirmed in this study; this is attributed to a photo-induced phase transition from amorphous carbon to diamond.

Mechanism of arsenate coprecipitation at the solid/liquid interface of ferrihydrite: A perspective review

Arsenate (As(V)) is a toxic element in acid mine drainage and has to be removed during the neutralization process. Coprecipitation with ferrihydrite is the main mechanism for As(V) removal from acid mine drainage. To improve treatment efficiency, a quantitative understanding of the coprecipitation mechanism is required. Coprecipitation can incorporate more As(V) into ferrihydrite than adsorption. The results of XRD (X-ray Diffraction) and XANES (X-ray Adsorption Near Edge Structure) analysis confirmed that the formation of poorly crystalline ferric arsenate increased when the initial As/Fe molar ratio increased in the coprecipitation with ferrihydrite. EXAFS (Extended X-ray Adsorption Fine Structure) analysis at the iron K-edge showed that the proportion of octahedral structures in ferrihydrite increased when the initial As/Fe molar ratio increased. Moreover, EXAFS analysis at the arsenic K-edge, assuming three kinds of surface complexes for the AsFe bond, revealed that the coordination number for AsFe with an atomic distance of 2.85 × 10−10 m increased and that for As-Fe with an atomic distance of 3.24 × 10−10 m decreased as the initial As/Fe molar ratio increased. Thus, for more efficient wastewater treatment, active control of coprecipitation phenomena according to mechanistic details is essential.