Continuous hydrogen regeneration through the oxygen vacancy control of metal oxides using microwave irradiation

The amount of hydrogen gas generated from metal oxide materials, based on a thermochemical water-splitting method, gradually reduces as the surface of the metal oxide oxidizes during the hydrogen generation process. To regenerate hydrogen, the oxygen reduction process of a metal oxide at high temperatures (1000–2500 °C) is generally required. In this study, to overcome the problem of an energy efficiency imbalance, in which the required energy of the oxygen reduction process for hydrogen regeneration is higher than the generated hydrogen energy, we investigated the possibility of the oxygen reduction of a metal oxide with a low energy using microwave irradiation. For this purpose, a macroporous nickel-oxide structure was used as a metal oxide catalyst to generate hydrogen gas, and the oxidized surface of the macroporous nickel-oxide structure could be reduced by microwave irradiation. Through this oxidation reduction process, ∼750 μmol g⁻¹ of hydrogen gas could be continuously regenerated. In this way, it is expected that oxygen-enriched metal oxide materials can be efficiently reduced by microwave irradiation, with a low power consumption of <∼4% compared to conventional high-temperature heat treatment, and thus can be used for efficient hydrogen generation and regeneration processes in the future.

Continuous hydrogen generation could be performed using microwave irradiation with polyvinylpyrrolidone for low energy reduction.     

Effect of polyvinylpyrrolidone (PVP) on palladium catalysts for direct synthesis of hydrogen peroxide from hydrogen and oxygen

When synthesizing nanoparticles in the liquid phase, polymeric materials (mainly polyvinylpyrrolidone, PVP) are applied as capping and/or stabilizing agents. The polymer layer on the nanoparticles must likely be removed since it blocks the active sites of the catalyst and inhibits mass transfer of the reactants. However, we have found that the polymer can have a positive effect on the direct synthesis of hydrogen peroxide. By testing Pd/SiO₂ catalysts with different amounts of PVP, it was revealed that an adequate amount of PVP resulted in a higher rate of hydrogen peroxide production (1001 mmol_H2O2 g_Pd⁻¹ h⁻¹) than pristine Pd/SiO₂ did (750 mmol_H2O2 g_Pd⁻¹ h⁻¹), unlike other PVP added Pd/SiO₂ catalysts containing excess PVP (less than 652 mmol_H2O2 g_Pd⁻¹ h⁻¹). The effect of PVP on the catalysts was examined by transmission electron microscopy, Fourier transform infrared spectroscopy, CO chemisorption, thermogravimetric analysis, and X-ray photoelectron spectroscopy. For the catalysts containing PVP, the oxidation state of the palladium 3d shifted to high binding energy due to electron transfer from Pd to the PVP molecules. Consequently, the presence of PVP on the catalysts inhibited oxygen dissociation and decomposition of the produced hydrogen peroxide, resulting in a high selectivity and high production rate of hydrogen peroxide.

Addition of polyvinylpyrrolidone to Pd/SiO₂ catalyst improved H₂O₂ selectivity by adjusting electronic state of palladium active species.     

Porous Pt–NiOx nanostructures with ultrasmall building blocks and enhanced electrocatalytic activity for the ethanol oxidation reaction

Oxidized species on surfaces would significantly improve the electrocatalytic activity of Pt-based materials. Constructing three-dimensional porous structures would endow the catalysts with good stability. Here, we report a simple strategy to synthesize porous Pt–NiO_x nanostructures composed of ultrasmall (about 3.0 nm) building blocks in an ethanol–water solvent. Structure and component analysis revealed that the as-prepared material consisted of interconnected Pt nanocrystals and amorphous NiO_x species. The formation mechanism investigation revealed that the preformed amorphous compounds were vital for the construction of porous structure. In the ethanol oxidation reaction, Pt–NiO_x/C exhibited current densities of 0.50 mA cm_Pt⁻² at 0.45 V (vs. SCE), which were 16.7 times higher than that of a commercial Pt/C catalyst. Potentiostatic tests showed that Pt–NiO_x/C had much higher current and better tolerance towards CO poisoning than the Pt/C catalyst under 0.45 V (vs. SCE). In addition, the NiO_x species on the surface also outperformed an alloyed Ni component in the test. These results indicate that the Pt–NiO_x porous nanomaterial is promising for use in direct ethanol fuel cells.

A porous Pt–NiO_x nanomaterial was constructed by a simple strategy to achieve excellent ethanol oxidation catalyst performance.     

Tailor-designed nanowire-structured iron and nickel oxides on platinum catalyst for formic acid electro-oxidation

This investigation is concerned with designing efficient catalysts for direct formic acid fuel cells. A ternary catalyst containing iron (nano-FeOx) and nickel (nano-NiOx) nanowire oxides assembled sequentially onto a bare platinum (bare-Pt) substrate was recommended for the formic acid electro-oxidation reaction (FAOR). While nano-NiOx appeared as fibrillar nanowire bundles (ca. 82 nm and 4.2 μm average diameter and length, respectively), nano-FeOx was deposited as intersecting nanowires (ca. 74 nm and 400 nm average diameter and length, respectively). The electrocatalytic activity of the catalyst toward the FAOR depended on its composition and loading sequence. The FeOx/NiOx/Pt catalyst exhibited ca. 4.8 and 1.6 times increases in the catalytic activity and tolerance against CO poisoning, respectively, during the FAOR, relative to the bare-Pt catalyst. Interestingly, with a simple activation of the FeOx/NiOx/Pt catalyst at −0.5 V vs. Ag/AgCl/KCl (sat.) in 0.2 mol L⁻¹ NaOH, a favorable Fe²⁺/Fe³⁺ transformation succeeded in mitigating the permanent CO poisoning of the Pt-based catalysts. Interestingly, this activated a-FeOx/NiOx/Pt catalyst had an activity 7 times higher than that of bare-Pt with an ca. −122 mV shift in the onset potential of the FAOR. The presence of nano-FeOx and nano-NiOx enriched the catalyst surface with extra oxygen moieties that counteracted the CO poisoning of the Pt substrate and electronically facilitated the kinetics of the FAOR, as revealed from CO stripping and impedance spectra.

A FeOx/NiOx/Pt catalyst was recommended for formic acid electro-oxidation; the essential anodic reaction in direct formic acid fuel cells.     

Role of polyvinylpyrrolidone in the electrochemical performance of Li2MnO3 cathode for lithium-ion batteries

While Li₂MnO₃ as an over-lithiated layered oxide (OLO) shows a significantly high reversible capacity of 250 mA h g⁻¹ in lithium-ion batteries (LIBs), it has critical issues of poor cycling performance and deteriorated high rate performance. In this study, modified OLO cathode materials for improved LIB performance were obtained by heating the as-prepared OLO at different temperatures (400, 500, and 600 °C) in the presence of polyvinylpyrrolidone (PVP) under an N₂ atmosphere. Compared to the as-prepared OLO, the OLO sample heated at 500 °C with PVP exhibited a high initial discharge capacity of 206 mA h g⁻¹ and high rate capability of 111 mA h g⁻¹ at 100 mA g⁻¹. The superior performance of the OLO sample heated at 500 °C with PVP is attributed to an improved electronic conductivity and Li⁺ ionic motion, resulting from the formation of the graphitic carbon structure and increased Mn³⁺ ratio during the decomposition of PVP.

The modified OLO cathode materials for improved LIB performance were obtained by heating the as-prepared OLO in the presence of polyvinylpyrrolidone (PVP) under an N₂ atmosphere.     

Comparison of NiOx thin film deposited by spin-coating or thermal evaporation for application as a hole transport layer of perovskite solar cells

We compared nickel oxide (NiO_x) deposited by thermal evaporation and that deposited by the spin-coating process, for use in the hole transport layers of inverted planar perovskite solar cells (PSCs). Spin-coating deposition for NiO_x HTL has been widely used, owing to its simplicity, low cost, and high efficiency. However, the spin-coating process has a technical limit to depositing a large-area uniformly. In contrast, thermal evaporation fabrication has a low price and is able to produce uniform and reproducible thin film. Hence, the chemical states, energy band alignment, surface morphologies, and microstructures of NiO_x deposited by spin coating and thermal evaporation were analyzed. The PSC with NiO_x HTL deposited by thermal evaporation showed a higher power conversion efficiency of 16.64% with open circuit voltage 1.07 V, short circuit current density of 20.68 mA cm⁻², and a fill factor of 75.51% compared to that of PSC with spin-coated NiO_x. We confirmed that thermal evaporation can deposit NiO_x to give a better performance as a HTL with higher reproducibility than spin-coating.

We compared nickel oxide (NiO_x) deposited by thermal evaporation and that deposited by the spin-coating process, for use in the hole transport layers of inverted planar perovskite solar cells (PSCs).     

Bilayer graphene/HgCdTe based very long infrared photodetector with superior external quantum efficiency,responsivity, and detectivity

We present a high-performance bilayer graphene (BLG) and mercury cadmium telluride (Hg_1−xCd_x=0.1867Te) heterojunction based very long wavelength infrared (VLWIR) conductive photodetector. The unique absorption properties of graphene enable a long carrier lifetime of charge carriers contributing to the carrier-multiplication due to impact ionization and, hence, large photocurrent and high quantum efficiency. The proposed p⁺-BLG/n-Hg_0.8133Cd_0.1867Te photodetector is characterized and analyzed in terms of different electrical and optical characteristic parameters using computer simulations. The obtained results are further validated by developing an analytical model based on drift-diffusion, tunneling and Chu''s methods. The photodetector has demonstrated a superior performance including improved dark current density (∼1.75 × 10⁻¹⁴ µA cm⁻²), photocurrent density (∼8.33 µA cm⁻²), internal quantum efficiency (QE_int ∼ 99.49%), external quantum efficiency (QE_ext ∼ 89%), internal photocurrent responsivity (∼13.26 A W⁻¹), external photocurrent responsivity (∼9.1 A W⁻¹), noise equivalent power (∼8.3 × 10⁻¹⁸ W), total noise current (∼1.06 fA), signal to noise ratio (∼156.18 dB), 3 dB cut-off frequency (∼36.16 GHz), and response time of 9.4 ps at 77 K. Furthermore, the effects of different external biasing, light power intensity, and temperature are evaluated, suggesting a high QE_ext of 3337.70% with a bias of −0.5 V near room temperature.

We present a high-performance bilayer graphene (BLG) and mercury cadmium telluride (Hg_1−xCd_x=0.1867Te) heterojunction based very long wavelength infrared (VLWIR) conductive photodetector.     

Facile synthesis of polypyrrole nanofiber (PPyNF)/NiOx composites by a microwave method and application in supercapacitors

In this study, polypyrrole nanofiber (PPyNF)/NiO_x composites were synthesized by a simple and fast microwave method. The samples were characterized using differential scanning calorimetry and thermal gravimetric analysis (DSC/TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Furthermore, the synthesized PPyNF/NiO_x nanocomposites were electrochemically characterized using galvanostatic charge–discharge, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques. They showed the highest specific capacitance of 657 F g⁻¹ at 0.5 A g⁻¹, demonstrating their potential application in supercapacitors.

In this study, polypyrrole nanofiber (PPyNF)/NiO_x composites were synthesized by a simple and fast microwave method.     

Efficient and stable perovskite solar cells using manganese-doped nickel oxide as the hole transport layer

Organic/inorganic hybrid perovskite solar cells (PSCs) have represented a promising field of renewable energy in recent years due to the compelling advantages of high efficiency, facile fabrication process and low cost. The development of inorganic p-type metal oxide materials plays an important role in the performance and stability of PSCs for commercial purposes. Herein a facile and effective way to improve hole extraction and conductivity of NiO_x films by manganese (Mn) doping is demonstrated in this study. A Mn-doped NiO_x layer was prepared by the sol–gel process and served as the hole transport layer (HTL) in inverted PSCs. The results suggest that Mn-doped NiO_x is helpful for the growth of perovskite layers with larger grains and higher crystallinity compared with the pristine NiO_x. Furthermore, the perovskite films deposited on Mn-doped NiO_x exhibit lower recombination and shorter carrier lifetime. The device based on 0.5 mol% Mn-doped NiO_x as the HTL displayed the best power conversion efficiency (PCE) of 17.35% and a high fill factor (FF) of 81%, which were significantly higher than those of the one using the pristine NiO_x HTL (PCE = 14.71%, FF = 73%). Moreover, the device retained 70% of its initial efficiency after 35 days'' storage under a continuous halogen lamp matrix exposure with an illumination intensity of 1000 W m⁻². Our results widen the development of PSCs for future production.

The device based on a Mn-doped NiO_x HTL retained 70% of its initial efficiency after 35 days’ storage under a continuous halogen lamp matrix exposure.     

Preparation and electrical properties of inorganic electride [Y2Ti2O6]2+(2e−)

Oxygen-depleted samples [Y₂Ti₂O_7−x]^2x+(2xe⁻) (0 ≤ x ≤ 1.0) were prepared by reducing Y₂TiO₇ powders at 500 °C to 650 °C using CaH₂ as a reductive agent, where x represents the content of , which was determined by thermogravimetric analysis. Powder X-ray diffraction patterns illustrate that the pure pyrochlore phase is kept for the samples with x ≤ 1.0, whereas the apparent x values surpass 1.0, and the impurity phase Y₂O₃ appears. The electride [Y₂Ti₂O_7−x]^2x+(2xe⁻) (x ≈ 1.0) can be obtained under a reductive condition, in which the concentration of V_O is 7.75 × 10²¹ cm⁻³. The electron paramagnetic resonance measurements gave the concentration of unpaired electrons in the electride as 1.30 × 10²¹ cm⁻³, indicating that the degree of the ionization of is less than 10%. Conductivity measurements for a sintered pellet sample (relative density ∼ 70%) indicate that the electride has quite high conductivity (∼1.09 S cm⁻¹ at 300 K). The conduction was interpreted by using the variable range hopping mechanisms.

Electride [Y₂Ti₂O₆]²⁺(2e⁻) was prepared by solid reducing processes, which was characterized by XRD, TG and EPR. The electride has high conductivity (1.09 S cm⁻¹ at 300 K).     

RuxSe@MoS2 hybrid as a highly efficient electrocatalyst toward hydrogen evolution reaction

Alkaline hydrogen evolution reaction (HER) requires highly efficient and stable catalytic materials, the engineering of which needs overall consideration of the water dissociation process as well as the intermediate hydrogen adsorption process. Herein, a Ru_xSe@MoS₂ hybrid catalyst was synthesized by the decoration of MoS₂ with Ru_xSe nanoparticles through a two-step hydrothermal reaction. Due to the bifunctionality mechanism in which Ru promotes the water dissociation and the nearby Se atoms, unsaturated Mo and/or S atoms act as active sites for the intermediate hydrogen adsorption, the hybrid catalyst exhibits an exceptional HER performance in basic media with a rather low overpotential of 45 mV at a current density of 10 mA cm⁻² and a small Tafel slope of 42.9 mV dec⁻¹. The synergetic effect between Ru_xSe and MoS₂ not only enables more catalytically active sites, but also increases the inherent conductivity of the hybrid catalyst, leading to more favorable HER kinetics under both alkaline and acidic conditions. As a result, Ru_xSe@MoS₂ also demonstrates an enhanced catalytic activity toward HER in 0.5 M H₂SO₄ in comparison with pure Ru_xSe and MoS₂, which requires an overpotential of 120 mV to deliver a 10 mA cm⁻² current density and gives a Tafel slope of 72.2 mV dec⁻¹. In addition, the hybrid electrocatalyst also exhibits superior electrochemical stability during the long-term HER process in both acidic media and alkaline media.

The bifunctionality mechanism of Ru_xSe@MoS₂ greatly enhances the alkaline HER performance, in which Ru promotes water dissociation and the nearby Se atoms, unsaturated Mo and/or S atoms act as active sites for the intermediate hydrogen adsorption.     

Facile preparation of ZnxCd1−xS/ZnS heterostructures with enhanced photocatalytic hydrogen evolution under visible light

Hydrogen evolution from water using solar energy is regarded as a most promising process, thus, exploring efficient photocatalysts for water splitting is highly desirable. To avoid the rapid recombination of photogenerated electrons and holes in CdZnS semiconductors, Zn_xCd_1−xS/ZnS composites were synthesized via a one-step hydrothermal method and then annealed at 400 °C for 60 min under argon flow. Zn_xCd_1−xS/ZnS composites are composed of ZnS nanosheets decorated with Zn_xCd_1−xS nanorods, and TEM and UV-vis absorption spectra confirm the formation of the heterostructure between Zn_xCd_1−xS nanorods and ZnS nanosheets. Because of the well-matched band alignment, stronger optical absorption and larger carrier density, Zn_0.2Cd_0.8S/ZnS has the highest hydrogen production, with a photocatalytic hydrogen production rate up to 16.7 mmol g⁻¹ h⁻¹ under visible light irradiation. Moreover, the photocatalyst also exhibits high stability and good reusability for hydrogen production reaction. The facile and efficient approach for ZnS based heterostructures could be extended to other metal compound materials.

Schematic illustration for electron charge transfer and H₂ evolution mechanism for the Zn_0.2Cd_0.8S/ZnS nanocomposites.     

In situ mass change and gas analysis of 3D manganese oxide/graphene aerogel for supercapacitors

Manganese oxide nanoparticles decorated on 3D reduced graphene oxide aerogels (3D MnO_x/rGO_ae) for neutral electrochemical capacitors were successfully produced by a rapid microwave reduction process within 20 s. The symmetric electrochemical capacitor of 3D MnO_x/rGO_ae (Mn 3.0 at%) storing charges via both electric double layer capacitance (EDLC) and pseudocapacitance mechanisms exhibits a specific capacitance of 240 F g⁻¹ as compared with 190 F g⁻¹ of that using the bare 3D rGO_ae at 0.5 A g⁻¹ in 1 M Na₂SO₄ (aq.) electrolyte. It retains 90% of the initial capacitance after 10 000 cycles, demonstrating high cycling stability. In addition, the charge storage mechanism of 3D MnO_x/rGO_ae was investigated using an electrochemical quartz crystal microbalance. In situ gas analysis using differential electrochemical mass spectrometry (DEMS) shows the CO₂ evolution at a cell potential over 1 V indicating that the positive electrode is possibly the voltage limiting electrode in the full cell. This finding may be useful for further development of practical high power and energy supercapacitors.

Manganese oxide nanoparticles decorated on 3D reduced graphene oxide aerogels (3D MnO_x/rGO_ae) for neutral electrochemical capacitors were successfully produced by a rapid microwave reduction process within 20 s.     

Unexpected visible light driven photocatalytic activity without cocatalysts and sacrificial reagents from a (GaN)1–x(ZnO)x solid solution synthesized at high pressure over the entire composition range

Optical and photocatalytic properties were determined for the solid solution series (GaN)_1–x(ZnO)_x synthesized at high pressure over the entire compositional range (x = 0.07 to 0.9). We report for the first time photocatalytic H₂ evolution activity from water for (GaN)_1–x(ZnO)_x without cocatalysts, pH modifiers and sacrificial reagents. Syntheses were carried out by reacting GaN and ZnO in appropriate amounts at temperatures ranging from 1150 to 1200 °C, and at a pressure of 1 GPa. ZnGa₂O₄ was observed as a second phase, with the amount decreasing from 12.8 wt% at x = 0.07 to ∼0.5 wt% at x = 0.9. The smallest band gap of 2.65 eV and the largest average photocatalytic H₂ evolution rate of 2.31 μmol h⁻¹ were observed at x = 0.51. Samples with x = 0.07, 0.24 and 0.76 have band gaps of 2.89 eV, 2.78 eV and 2.83 eV, and average hydrogen evolution rates of 1.8 μmol h⁻¹, 0.55 μmol h⁻¹ and 0.48 μmol h⁻¹, respectively. The sample with x = 0.9 has a band gap of 2.82 eV, but did not evolve hydrogen. An extended photocatalytic test showed considerable reduction of activity over 20 hours.

(GaN)_1–x(ZnO)_x synthesized at high pressure produces H₂ in the presence of visible light without any cocatalysts or sacrificial reagents.     

2D TiVCTx layered nanosheets grown on nickel foam as highly efficient electrocatalysts for the hydrogen evolution reaction

Exploring highly efficient and durable catalysts for the hydrogen evolution reaction (HER) is crucial for the hydrogen economy and environmental protection issues. Numerous studies have now found that transition metal carbide MXenes are ideal candidates as catalysts for the hydrogen evolution reaction. However, MXenes are inclined to easily undergo lamellar structure agglomeration and stacking, which impedes their further applications. Besides, most of the extant research has focused on single transition metal carbides, and the investigation of double transition metal carbide MXenes is rather rare. In this research work, a three-dimensional (3D) TiVCT_x-based conductive electrode was constructed by depositing 2D TiVCT_x nanosheets on 3D network structured nickel foam (NF) to synthesize a hybrid electrode material (abbreviated as TiVCT_x@NF). TiVCT_x@NF exhibits efficient electrochemical properties with a low overpotential of 151 mV at 10 mA cm⁻² and a small Tafel slope of 116 mV dec⁻¹. Benefitting from the open layer structure and strong interfacial coupling effect, compared to the pristine structure, the resulting TiVCT_x@NF has greatly increased active sites for the hydrogen evolution reaction (HER) and encounters less resistance for charge transfer. In addition, TiVCT_x@NF exhibits better stability in long-term acidic electrolytes. This work provides a tactic to prepare three-dimensional network electrode materials and broadens the application of single transition metal carbide MXenes as water splitting electrodes in the HER, which is beneficial to the application of noble metal-free electrocatalysts.

The TiVCT_x MXene was obtained by etching and peeling methods, and the TiVCT_x@NF hybrid electrode material was obtained by the deposition method. The electrochemical performance was evaluated using a variety of characterization methods.     

A 3D nitrogen-doped graphene aerogel for enhanced visible-light photocatalytic pollutant degradation and hydrogen evolution

Three-dimensional (3D) graphene-based aerogels have attracted widespread interest as promising photocatalysts for dye degradation and hydrogen production. Herein, we have developed a 3D nitrogen-doped graphene aerogel (3DNG) from graphitic carbon nitride combined with graphene oxide (GO). The nitrogen dopant in the 3D aerogel was achieved via a thermal treatment at 1000 °C, and the 3D aerogel catalyst could retain its 3D porous structure after the thermal treatment. The 3DNG was characterized via FTIR, Raman, TEM, UV-vis, XPS spectroscopies and BET analysis, and the results indicated that this 3DNG with a large surface area of 536 m² g⁻¹ and a band gap of 2.42 eV demonstrated a high adsorption capacity and enhanced methylene blue degradation and hydrogen production under visible light irradiation. Characterization also identified that the porous 3D structure with hydrogen bonding and π–π interactions and better charge transfer resulting from the nitrogen doping are the major reasons for the enhanced photocatalytic performance over this 3DNG catalyst.

The synergistic effect of the 3D structure and N-doping explain the high surface area of 536 m² g⁻¹ and excellent photocatalytic activity.     

The sensitive detection of methylene blue using silver nanodecahedra prepared through a photochemical route

In this work, we have carried out systematic studies on the critical role of polyvinyl pyrrolidone (PVP) and citrate in the well-known chemical reduction route to synthesize silver nanodecahedra (AgND). Silver nitrate (AgNO₃) was used as silver source, which can be directly converted to metallic silver after being reduced by sodium borohydride (NaBH₄) under blue light-emitting diode (LED) irradiation (λ_max = 465 nm), and polyvinyl pyrrolidone (PVP) as a capping agent to assist the growth of AgND. The obtained products were silver nanodecahedra of excellent uniformity and stability with high efficiency and yield. The results showed that PVP acted as a capping agent to stabilize the silver nanoparticles, prolonging the initiation time required for nanodecahedra nucleation, thus inducing anisotropic growth, allowing the size and morphology of the AgND to be controlled successfully. This improved understanding allows a consistent process for the synthesis of AgND with significantly enhanced reproducibility to be developed and the formation mechanism of these nanostructures to be elucidated. This is a simple, cost-effective and easily reproducible method for creating AgND. The typical absorption maxima in the UV-vis spectroscopy of Ag seeds was λ_max ∼400 nm and that of AgND was λ_max ∼480 nm. The size of the prepared AgND was in the range of 60–80 nm. SEM images confirmed the uniform and high density of AgND when the concentration of PVP was 0.5 mM. The XRD pattern showed that the final product of AgND was highly crystallized. In addition, the prepared AgND can be used to detect methylene blue (MB) in a sensitive manner with good reproducibility and stability using Surface-Enhanced Raman Scattering (SERS) phenomenon. Out of the obtained products, the AgND prepared with 50 min blue LED light irradiation (AgND-50) displayed the strongest SERS signal. Interestingly, MB in diluted solution can be detected with a concentration as low as 10⁻⁷ M (the limit of detection, LOD) and the linear dependence between SERS intensity and the MB concentration occurred in the range from 10⁻⁷ to 10⁻⁶ M. The enhancement factor (EF) of the SERS effect was about 1.602 × 10⁶ with a MB concentration of 10⁻⁷ M using 532 nm laser excitation.

In this work, we have carried out systematic studies on the critical role of polyvinyl pyrrolidone (PVP) and citrate in the well-known chemical reduction route to synthesize silver nanodecahedra (AgND).     

Structural exploration of AuxM− (M = Si,Ge, Sn; x = 9–12) clusters with a revised genetic algorithm

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters. The most interesting finding in the structural study of Au_xSi⁻ (x = 9–12) is the 3D (Au₉Si⁻ and Au₁₀Si⁻) → quasi-planar 2D (Au₁₁Si⁻ and Au₁₂Si⁻) structural evolution of the Si-doped clusters, which reflects the competition of Au–Au interactions (forming a 2D structure) and Au–Si interactions (forming a 3D structure). The Au_xM⁻ (x = 9–12; M = Ge, Sn) clusters have quasi-planar structures, which suggests a lower tendency of sp³ hybridization and a similarity of electronic structure for the Ge or Sn atom. Au₉Si⁻ and Au₁₀Si⁻ have a 3D structure, which can be viewed as being built from Au₈Si⁻ and Au₉Si⁻ with an extra Au atom bonded to a terminal gold atom, respectively. In contrast, the quasi-planar structures of Au_xM⁻ (x = 9–12; M = Ge, Sn) reflect the domination of the Au–Au interactions. Including the spin–orbit (SO) effects is very important to calculate the simulated spectrum (structural fingerprint information) in order to obtain quantitative agreement between theoretical and future experimental PES spectra.

We used a revised genetic algorithm (GA) to explore the potential energy surface (PES) of Au_xM⁻ (x = 9–12; M = Si, Ge, Sn) clusters.     

Electrocatalytic water oxidation by a Ni(ii) salophen-type complex

A new mononuclear Ni(ii) complex, NiL (1), was synthesized from the reaction of Ni(OAc)₂·4H₂O and salophen-type N₂O₂-donor ligand, H₂L (where H₂L = 2,2′-((1E,1′E)-((4-chloro-5-methyl-1,2-phenylene)bis(azanylylidene))bis(methanylylidene))diphenol), in ethanol. The obtained complex was characterized by elemental analysis, spectroscopic techniques and single crystal X-ray analysis. The complex was studied as a water oxidizing catalyst and its electrocatalytic activity in the water oxidation reaction was tested in 0.5 M of borate buffer at pH = 3, 7 and 11 in a typical three-electrode setup with a carbon paste electrode modified by complex 1 as a working electrode. The linear sweep voltammetry (LSV) curves indicated that complex 1 has a much superior activity and only needs 21 mV vs. Ag/AgCl overvoltage to reach a geometrical catalytic current density of 2.0 mA cm⁻² at pH = 11. The onset potential decreased from 1.15 V to 0.67 V vs. Ag/AgCl with an increase of pH from 3 to 13 under a constant current density of 1.0 mA cm⁻². Then, to determine the true catalyst for the water oxidation reaction in the presence of complex 1 at pH = 3, 7 and 11, cyclic voltammetry was also performed. The continuous CVs for complex 1 at neutral and alkaline solutions showed significant progress for the water oxidation reaction. In addition, the amperometry tests exhibited excellent stability and high constant current density for water oxidation by CPE-complex 1 under electrochemical conditions at pH = 11 and 7. Although X-ray powder diffraction analysis did not show a pure and crystalline structure for NiO_x, the scanning electron microscopy images showed that nickel oxide at pH = 11 and nickel oxide or other Ni-based compounds at pH = 7 are true water oxidizing catalysts on the surface of a CPE electrode. Moreover at pH = 3, no clear water oxidation or NiO_x formation was observed.

One new Ni-salophen type complex was designed as a water oxidation electrocatalyst in neutral and basic solutions.     

In-plasma-catalysis for NOx degradation by Ti3+ self-doped TiO2−x/γ-Al2O3 catalyst and nonthermal plasma

In an attempt to realize the efficient treatment of NO_x, a mixed catalyst of Ti³⁺ self-doped TiO_2−x and γ-Al₂O₃ was constructed by reducing commercial TiO₂. The degradation effect on NO_x was evaluated by introducing the mixed catalyst into a coaxial dual-dielectric barrier reactor. It was found that the synthesized TiO_2−x could achieve considerable degradation effects (84.84%, SIE = 401.27 J L⁻¹) in a plasma catalytic system under oxygen-rich conditions, which were better than those of TiO₂ (73.99%) or a single plasma degradation process (26.00%). The presence of Ti³⁺ and oxygen vacancies in TiO_2−x resulted in a relatively narrow band gap, which contributed to catalyzing deeply the oxidation of NO_x to NO₂⁻ and NO₃⁻ during the plasma-induced “pseudo-photocatalysis” process. Meanwhile, the TiO_2−x showed an improved discharge current and promoted discharge efficiency, explaining its significant activation effect in the reaction. Reduced TiO_2−x could achieve an impressive degradation effect in a long-time plasma-catalysis process, and still maintained its intrinsic crystal structure and morphology. This work provides a facile synthesis procedure for preparing Ti³⁺ self-doped TiO_2−x with practical and scalable production potential; moreover, the novel combination with plasma also provides new insights into the low-temperature degradation of NO_x.

TiO_2−x has a smaller forbidden band width, more abundant Ti³⁺ and oxygen vacancies, so as to obtain a better and more stable degradation effect of NO_x in plasma-catalysis process.