Extensive enhancement in power conversion efficiency of dye-sensitized solar cell by using Al-doped TiO<Subscript>2</Subscript> photoanode

In this work, we have prepared Al-doped TiO₂ nanoparticles via a hydrothermal method and used it for making photoanode in dye-sensitized solar cell (DSSC). Material characterizations were done using XRD, AFM, SEM, TEM and EDAX. XPS results reveal that Al is introduced successfully into the structure of TiO₂ creating new impurity energy levels in the forbidden gap. This resulted in tuning of the conduction band of TiO₂ and reduced charge recombination which led to better current conversion efficiency of DSSC. Greater dye loading and enhanced surface area was obtained for Al-doped TiO₂ compared to un-doped TiO₂. I-V analysis, EIS and Bode plots are employed to evaluate photovoltaic performance. The short-circuit current density (J _sc) and efficiency (η) of cell employing Al-doped TiO₂ photoanode were extensively enhanced compared to the cell using un-doped TiO₂. The optical band gap (E _g) for Al-doped and un-doped TiO₂ was obtained as 2.8 and 3.2 eV, respectively. J _sc and η were 13.39 mAcm^?2 and 4.27%, respectively, under illumination of 100 mWcm^?2 light intensity when thin films of 1% Al-doped TiO₂ was employed as photoanode in DSSC using N719 as the sensitizer dye. With the use of un-doped TiO₂ as photoanode under similar conditions, J _sc 5.12 mAcm^?2 and η 1.06% only could be obtained. The maximum IPCE% obtained with Al-doped TiO₂ and un-doped TiO₂ was 67 and 38% respectively at the characteristic wavelength of dye (λ _max = 540 nm). The EIS analyses revealed resistive and capacitive elements that provided an insight into various interfacial processes in terms of the charge transport. It was observed that Al-doping reduced the interfacial resistance leading to better charge transport which has improved both photocurrent density and conversion efficiency. Higher electron mobility and fast diffusion resulting in greater charge collection efficiency was obtained for Al-doped TiO₂ compared to the un-doped TiO₂. Using the Mott–Schottky plot, the donor density was calculated for un-doped and Al-doped TiO₂. The work demonstrated that the Al-doped TiO₂ is potential photoanode material for low-cost and high-efficiency DSSC.     

Interlaced polyaniline/carbon nanotube nanocomposite co-electrodeposited on TiO<Subscript>2</Subscript> nanotubes/Ti for high-performance supercapacitors

A series of PANI-CNTs/TiO₂ nanotubes/Ti electrodes were fabricated via pulse current co-electrodeposition of polyaniline and functionalized carbon nanotubes onto TiO₂ nanotubes/Ti electrodes. FT-IR spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy were applied in order to characterize the modified TiO₂ nanotubes/Ti electrodes. The morphology studies showed that the PANI-CNTs/TiO₂ nanotubes/Ti nanocomposite electrode has many interlaced PANI-CNTs nanorods on the surface of TiO₂ nanotubes. The electrochemical measurements of the modified electrodes confirmed that the CNTs in the composite can significantly improve the capacitive behavior as well which have been compared with that of PANI/TiO₂ nanotubes/Ti electrodes. The modified electrode exhibited much higher specific capacitance (190 mF cm^?2 with 90% retention after 1000 cycles) compared to the PANI/TiO₂ nanotubes/Ti (70 mF cm^?2 with 77% retention after 1000 cycles) at a current density of 0.85 mA cm^?2, indicating its great potential for supercapacitor applications.

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Graphical abstract Interlaced polyaniline/carbon nanotube nanocomposite electrodeposited on TiO₂ nanotubes/Ti

     

A high mass loading electrode based on ultrathin Co<Subscript>3</Subscript>S<Subscript>4</Subscript> nanosheets for high performance supercapacitor

There is a growing need for the electrode with high mass loading of active materials, where both high energy and high power densities are required, in current and near-future applications of supercapacitor. Here, an ultrathin Co₃S₄ nanosheet decorated electrode (denoted as Co₃S₄/NF) with mass loading of 6 mg cm^?2 is successfully fabricated by using highly dispersive Co₃O₄ nanowires on Ni foam (NF) as template. The nanosheets contained lots of about 3～5 nm micropores benefiting for the electrochemical reaction and assembled into a three-dimensional, honeycomb-like network with 0.5～1 μm mesopore structure for promoting specific surface area of electrode. The improved electrochemical performance was achieved, including an excellent cycliability of 10,000 cycles at 10 A g^?1 and large specific capacitances of 2415 and 1152 F g^?1 at 1 and 20 A g^?1, respectively. Impressively, the asymmetric supercapacitor assembled with the activated carbon (AC) and Co₃S₄/NF electrode exhibits a high energy density of 79 Wh kg^?1 at a power density of 151 W kg^?1, a high power density of 3000 W kg^?1 at energy density of 30 Wh kg^?1 and 73 % retention of the initial capacitance after 10,000 charge-discharge cycles at 2 A g^?1. More importantly, the formation process of the ultrathin Co₃S₄ nanosheets upon reaction time is investigated, which is benefited from the gradual infiltration of sulfide ions and the template function of ultrafine Co₃O₄ nanowires in the anion-exchange reaction.

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Graphical abstract The ultrathin 2D Co₃S₄ nanosheets fabricated on 3D Ni foam and the formation process of the ultrathin Co₃S₄ nanosheets upon reaction times has been investigated. At the same time, the Co₃S₄/NF electrode displays an outstanding specific capacitance of 2420 F g^?1 at 1 A g^?1 with high mass loading of 6 mg cm^?2.

     

Fabrication and characterisation of a mixed oxide-covered mesh electrode composed of NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> and its capability of generating hydroxyl radicals during the oxygen evolution reaction in electrolyte-free water

A mixed oxide-covered mesh electrode composed of NiCo₂O₄ (MOME-NiCo₂O₄) was prepared on a stainless-steel substrate using thermal decomposition (slow-cooling rate method). Surface, bulk and electrochemical properties of MOME were studied using different techniques, namely scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry (CV) with determination of the electrochemical porosity (?) and morphology factor (φ) parameters, quasi-stationary polarisation curves (PC) and electrochemical impedance spectroscopy (EIS). SEM images revealed a good coverage of the metallic wires by a compact oxide layer (absence of cracks). XRD analysis confirmed the formation of the spinel NiCo₂O₄ with the presence of NiO. The ‘in situ’ surface parameters denoted as ? and φ exhibited values of 0.39 and 0.33, respectively, revealing that the electrochemically active surface area is mainly confined to the ‘outer/external’ surface regions of the oxide layer. The PC was characterised by two Tafel slopes distributed in the low (b ₁ = 46 mV dec^?1) and high (b ₂ = 59 mV dec^?1) overpotential domains. The corresponding apparent exchange current densities were j ₀₍₁₎ = (3.43 ± 0.11) × 10^?6 A cm^?2 and j ₀₍₂₎ = (6.70 ± 0.08) × 10^?6 A cm^?2, respectively. The EIS study accomplished in the low-overpotential domain revealed a Tafel slope (b ₁) of 51 mV dec^?1. According to the spin-trapping reaction using N,N-dimethyl-p-nitrosoaniline (RNO), the MOME-NiCo₂O₄ electrode exhibited good performance for the generation of weakly adsorbed hydroxyl radicals (HO^?) during the OER in electrolyte-free water.     

Synthesis and characterization of a new monophosphate (C<Subscript>6</Subscript>H<Subscript>16</Subscript>N<Subscript>2</Subscript>)(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Chemical preparation, crystal structure, and NMR spectroscopy of a new trans-2,5-dimethylpiperazinium monophosphate are given. This new compound crystallizes in the triclinic system, with the space group P-1 and the following parameters: a = 6.5033(3), b = 7.6942(4), c = 8.1473(5) Å, α = 114.997(3), β = 92.341(3), γ = 113.136(3), V = 329.14(3) ų, Z = 1, and D_x = 1.565 g cm^?3. The crystal structure has been determined and refined to R = 0.030 and R _w(F ²) = 0.032 using 1558 independent reflections. The structure can be described as infinite [H₂PO₄] _n ^n? chains with (C₆H₁₆N₂)²⁺ organic cations anchored between adjacent polyanions to form columns of anions and cations running along the b axis. This compound has also been investigated by IR, thermal, and solid-state, ¹³C and ³¹P MAS NMR spectroscopies and Ab initio calculations.     

Hydrothermally synthesized Ni(OH)<Subscript>2</Subscript>@Zn(OH)<Subscript>2</Subscript> composite with enhanced electrochemical performance for supercapacitors

Two kinds of electrode materials Ni(OH)₂ and Ni(OH)₂@Zn(OH)₂ composite are fabricated on nickel foam. Electrochemical experiments indicate Ni(OH)₂@Zn(OH)₂ composite deserves further study due to high specific capacitance and good cycle stability, so that it can achieve energy storage and conversion as much as possible. When the hydrothermal time is different, the electrochemical performance of the sample is also different. Accurately, samples can obtain better electrochemical performance at 15 h, and the maximum specific capacitance of Ni(OH)₂@Zn(OH)₂ is 7.87 F cm^?2 compared to Ni(OH)₂ (0.61 F cm^?2) at 5 mA cm^?2. Even at 50 mA cm^?2, specific capacitance is 5.24 F cm^?2 and rate capability is 66.6%. Furthermore, Ni(OH)₂@Zn(OH)₂-15 h loses 19.8% after 1000 cycles, revealing the composite has an outstanding stable cycle. These properties also indicate Ni(OH)₂@Zn(OH)₂-15 h is a promising electrode material.     

Carbon ceramic electrodes modified with mixed oxides SiO<Subscript>2</Subscript>/SnO<Subscript>2</Subscript> for determination of levofloxacin

The preparation of a carbon ceramic electrode modified with SnO₂ (CCE/SnO₂) using tin dibutyl diacetate as precursor was optimized by a 2³ factorial design. The factors analyzed were catalyst (HCl), graphite/organic precursor ratio, and inorganic precursor (dibutyltin diacetate). The statistical treatment of the data showed that only the second-order interaction effect, catalyst × inorganic precursor, was significant at 95% confidence level, for the electrochemical response of the system. The obtained material was characterized by scanning electron microscopy (MEV), X-ray diffraction (XRD), RAMAN spectroscopy, XPS spectra, and voltammetric techniques. From the XPS spectra, it was confirmed the formation of the Si–O–Sn bond by the shift in the binding energy values referred to Sn 3d3/2 due to the interaction of Sn with SiOH species. The incorporation of SnO₂ provided an increment of the electrode response for levofloxacin, with Ipa = 147.0 μA for the ECC and Ipa = 228.8 μA for ECC/SnO₂, indicating that SnO₂ when incorporated into the silica network enhances the electron transfer process. Under the optimized working conditions, the peak current increased linearly with the levofloxacin concentration in the range from 6.21×10^?5 to 6.97×10^?4 mol L^?1 with quantification and detection limits of 3.80×10^?5 mol L^?1 (14.07 mg L^?1) and 1.13×10^?5 mol L^?1 (4.18 mg L^?1), respectively.     

Kinetics of Na|CF<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and Li|CF<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> systems

Properties of CF _x /Li and CF _x /Na cells were examined while using galvanostatic charging/discharging, electrochemical impedance spectroscopy and scanning electron microscopy (SEM). The capacity during the first cycle was as high as ca. 1000 mAh g^?1. Such an electrode is suitable for primary CF _x /Li and CF _x /Na batteries. SEM images of CF _x cathode showed that during discharging it was transformed into amorphous carbon and LiF or NaF crystals (of diameter of ca. 5–20 μm). These systems (C?+?LiF or C?+?NaF) cannot be reversibly converted back into CF _x /Li or CF _x /Na, respectively. Exchange current densities are between 10^?7 Acm^?2 and 10^?9 Acm^?2 when working with LiPF₆ and NaPF₆ electrolytes (1.12?×?10^?7 Acm^?2 and 6.82?×?10^?9 Acm^?2, respectively). Those values are low and indicate that the charge transfer process may be the rate-determining step. Activation energies for the charge transfer process were 57 and 72 kJ mol^?1 for CF _x /LiPF₆ and CF _x /NaPF₆ systems, respectively. Higher activation energy barrier for the CF/Na⁺?+?e^??→?C?+?NaF reaction results in lower observed exchange current density in comparison to the system with lithium ions.     

Synthesis and thermal decomposition of neodymium(III) peroxotitanate to Nd<Subscript>2</Subscript>TiO<Subscript>5</Subscript>

Neodymium(III) peroxotitanate is used as a precursor for obtaining Nd₂TiO₅. The last one possesses numerous valuable electrophysical properties. TiCl₄, Nd(NO₃)₃·6H₂O and H₂O₂ in mol ratio 1:2:10 were used as starting materials. The reaction ambience was alkalized to pH = 9 with a solution of NH₃. The obtained neodymium(III) peroxotitanate and intermediate compounds of the isothermal heating were proved by the help of quantitative analysis and infrared spectroscopy (IRS). It has Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O composition. The absorption band observed in IRS at 831 cm^?1 relates to a triangular bonding of the peroxo group of Ti, at 1062 cm^?1—terminal groups Ti–OH and at 1491 and 1384 cm^?1—the bridging OH^?-groups Ti–O(H)–Ti. Nd₂TiO₅ was obtained by thermal decomposition of neodymium(III) peroxotitanate. The isothermal conditions for decomposition were determined on the base of differential thermal analysis, thermogravimetric and differential scanning calorimetry results in the temperature range of 20–1000 °C. The mechanism of thermal decomposition of Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O to Nd₂TiO₅ was studied. In the temperature range of 20–208 °C, a simultaneous decomposition of the peroxo groups by the separation of oxygen and hydrate water is conducted and Nd₄[Ti₂O₄(OH)₁₂] is obtained. From 208 to 390 °C, the terminal OH^?-groups are separated and Nd₄[Ti₂O₇(OH)₆] is formed. In the range of 390–824 °C, the bridging OH^?-groups are completely decomposed to Nd₂TiO₅. The optimal conditions for obtaining nanocrystalline Nd₂TiO₅ are 900 °C for 6 h and 20–80 nm.     

Degradation of ofloxacin by UVA-LED/TiO<Subscript>2</Subscript> nanotube arrays photocatalytic fuel cells

The degradation of ofloxacin (OFX) at low concentration in aqueous solution by UVA-LED/TiO₂ nanotube arrays photocatalytic fuel cells (UVA-LED/TiO₂ NTs PFCs) was investigated. TiO₂ nanotube arrays (TiO₂ NTs) photoanode prepared by anodization-constituted anatase–rutile bicrystalline framework. The results indicated that the degradation efficiency of OFX by UVA-LED/TiO₂ NTs PFC was significantly enhanced by 14.3% compared with UVA-LED/TiO₂ NTs photocatalysis. The pH affected the degradation efficiency markedly; the highest degradation efficiency (95.0%) and the pseudo-first-order reaction rate constant k value (0.049 min^?1) were achieved in neutral condition (pH 7.0). The degradation efficiency increased with the increasing concentration of dissolved oxygen (DO) in the UVA-LED/TiO₂ NTs PFC. The main reactive species of OFX degradation are positive holes (h⁺) and superoxide ion radicals (O ₂ ^·? ) in a DO sufficient condition. Furthermore, the possible pathways of OFX degradation were proposed.     

Simple and rapid synthesis of ternary polyaniline/titanium oxide/graphene by simultaneous TiO<Subscript>2</Subscript> generation and aniline oxidation as hybrid materials for supercapacitor applications

This paper reports a simple methodology for the synthesis of a polyaniline/titanium oxide/graphene hybrid (Pani/TiO₂/GN) using a simple methodology, and their application as a supercapacitor electrode material for energy storage. The Pani/TiO₂/GN hybrid was prepared by a simple approach by simultaneous generation of Pani and TiO₂ in situ from aniline and titanium iso-propoxide, respectively, in the presence of GN under ice bath conditions. The incorporation of GN improved the electrical conductivity of Pani and helped to decrease the charge transfer resistance, whereas TiO₂ generation by an in situ method increased the surface area considerably and enhanced the capacitance of the Pani/TiO₂/GN hybrid. TEM showed that Pani and TiO₂ were well incorporated and coated on the GN successfully. The shift of the peaks in the FTIR spectrum and XRD pattern of the Pani/TiO₂/GN hybrid compared to their pure counterparts suggested that TiO₂ and Pani had been perfectly coated on the GN, and there was a strong interaction among Pani, GN, and TiO₂ particles. The electrochemical performance of the as-prepared Pani/TiO₂/GN hybrid electrode showed a high specific capacitance of 403.2 F g^?1 at a current density of 2 A g^?1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO₂ into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cyclic stability of the Pani/TiO₂/GN hybrid, leading to superior electrochemical performance.

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Graphical abstract The electrochemical performance of as-prepared Pani/TiO₂/GN hybrid electrode showed a high specific capacitance of 403.2 F g^?-1 at a current density of 2 A g^?-1 and excellent cycling stability for up to 1000 cycles. This suggested that the effective incorporation of GN and TiO₂ into Pani and the high surface area could simultaneously increase the electrochemical capacitance and cycle stability of the Pani/TiO₂/GN hybrid, leading to superior electrochemical performance.

     

Hydrothermal synthesis of brookite TiO<Subscript>2</Subscript> nanoparticles for dye-sensitized solar cell

We obtained Tannin-4-azobenzoic acid (azo dye) by the conventional method of diazotization and coupling of aromatic amines. The properties of the azo dye were characterized via ultraviolet-visible (UV–vis), infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy. Nanocrystalline titanium dioxide (TiO₂) thin films were deposited by hydrothermal method onto fluorine-doped tin (IV) oxide (FTO)-coated glass substrate at 353 K for 4 h. The as-deposited and annealed films were characterized for structural, morphological, optical, thickness, and wettability properties. The synthesized metal free azo dye was used to sensitize the prepared TiO₂ thin film with thickness of 26 μm. The photoelectrochemical (PEC) performance of TiO₂ sensitized with the azo dye was evaluated in polyiodide (0.1 M KI + 0.01 M I₂ + 0.1 M KCl) electrolyte at 40 mW cm^?2 illumination intensity. The cell yielded a short circuit current of 2.82 mA, open circuit voltage of 314.3 mV, a fill factor of 0.30, and a photovoltaic conversion efficiency value of 0.64%.

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Graphical abstract ?

     

Kinetics of Li-ion transfer reaction at LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>, LiCoO<Subscript>2</Subscript>, and LiFePO<Subscript>4</Subscript> cathodes

Kinetics of LiFePO₄, LiMn₂O₄, and LiCoO₂ cathodes operating in 1 M LIPF₆ solution in a mixture of ethylene carbonate and dimethyl carbonate was deduced from impedance spectra taken at different temperatures. The most striking difference of electrochemical impedance spectroscopy (EIS) curves is the impedance magnitude: tens of ohms in the case of LiFePO₄, hundreds of ohms for LiMn₂O₄, and thousands of ohms for LiCoO₂. Charge transfer resistances (R _ct) for lithiation/delitiation processes estimated from the deconvolution procedure were 6.0 Ω (LiFePO₄), 55.4 Ω (LiCoO₂), and 88.5 Ω (LiMn₂O₄), respectively. Exchange current density for all the three tested cathodes was found to be comparable (0.55–1·10^?2 mAcm^?2, T = 298 K). Corresponding activation energies for the charge transfer process, \( {E}_{ct}^{\#} \), differed considerably: 66.3, 48.9, and 17.0 kJmol^?1 for LiMn₂O₄, LiCoO₂, and LiFePO₄, respectively. Consequently, temperature variation may have a substantial influence on exchange current densities (j _o) in the case of LiMn₂O₄ and LiCoO₂ cathodes.     

Thermal properties,phase transitions,vibrational and reorientational dynamics of [Mn(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>

[Mn(NH₃)₆](NO₃)₂ crystallizes in the cubic, fluorite (C1) type crystal lattice structure (Fm \( \overline{3} \) m) with a = 11.0056 Å and Z = 4. Two phase transitions of the first-order type were detected. The first registered on DSC curves as a large anomaly at T _C1 ^h  = 207.8 K and T _C1 ^c  = 207.2 K, and the second registered as a smaller anomaly at T _C2 ^h  = 184.4 K and T _C2 ^c  = 160.8 K (where the upper indexes h and c denote heating and cooling of the sample, respectively). The temperature dependence of the full width at half maximum of the band associated with the δ_s(HNH)F_1u mode suggests that the NH₃ ligands in the high temperature and intermediate phase reorientate quickly with correlation times in the order of several picoseconds and with activation energy of 9.9 kJ mol^?1. In the phase transition at T _C2 ^c probably only a some of the NH₃ ligands stop their reorientation, while the remainders continue to reorientate quickly with activation energy of 7.7 kJ mol^?1. Thermal decomposition of the investigated compound starts at 305 K and continues up to 525 K in four main stages (I–IV). In stage I, ²/₆ of all NH₃ ligands were seceded. Stages II and III are connected with an abruption of the next ²/₆ and ¹/₆ of total NH₃, respectively, and [Mn(NH₃)](NO₃)₂ is formed. The last molecule of NH₃ per formula unit is freed at stage IV together with the simultaneous thermal decomposition of the resulting Mn(NO₃)₂ leading to the formation of gaseous products (O₂, H₂O, N₂ and nitrogen oxides) and solid MnO₂.     

Ni<Subscript>0.37</Subscript>Co<Subscript>0.63</Subscript>S<Subscript>2</Subscript>-reduced graphene oxide nanocomposites for highly efficient electrocatalytic oxygen evolution and photocatalytic pollutant degradation

A series of Ni_0.37Co_0.63S₂-reduced graphene oxide nanocomposites with different graphene contents (NCS@rGO-x) has been successfully prepared via a facile one-step hydrothermal method and applied as the catalysts for the oxygen evolution reaction (OER) and degradation of organic pollutants. The XRD and FESEM analyses revealed that the phase structure and morphology of NCS nanoparticles were substantially influenced by the graphene contents. The phase structure of NCS nanoparticles gradually transformed from primary NiCo₂S₄ to Ni_0.37Co_0.63S₂ and the morphology and size of NCS nanoparticles were found to become more regular and homogeneous with the increase of graphene concentration. On the NCS@rGO-x nanocomposites, the NCS@rGO-2 sample demonstrated the best catalytic activity toward the OER, which delivers a stable current density of 10 mA cm^?2 at a small overpotential of ～276 mV (vs. RHE) with a Tafel slope as low as 48 mV dec^?1. Furthermore, the NCS@rGO-2 sample showed the remarkable photocatalytic activity for degradation of methylene blue (MB), which may be attributed to the increased reaction sites and high separation efficiency of photogenerated charge carries due to the electronic interaction between NCS nanoparticles and rGO. All these impressive performances indicate that the NCS@rGO-2 nanocomposite is a promising catalyst in energy and environmental fields.

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Graphical abstract A series of Ni_0.37Co_0.63S₂-reduced graphene oxide nanocomposites with different graphene contents has been successfully prepared and applied as the catalysts for the oxygen evolution reaction (OER) and degradation of organic pollutants. The NCS@rGO-2 catalyst-modified stainless steel wire mesh (SSWM) electrode delivers a stable current density of 10 mA cm^?2 at a small overpotential of ～276 mV (vs. RHE) with a Tafel slope as low as 48 mV dec^?1. At the same time, the NCS@rGO-2 catalyst is also first investigated as an efficient photocatalyst for degradation of MB.

     

Simultaneous determination of trimethylamine,formaldehyde and benzene via the cataluminescence of In<Subscript>3</Subscript>LaTi<Subscript>2</Subscript>O<Subscript>10</Subscript> nanoparticles

The authors describe a cataluminescence (CTL) based sensing method via signals generated at the surface of In₃LaTi₂O₁₀ nanoparticles for simultaneous determination of trimethylamine, formaldehyde and benzene in air. The analytical wavelengths are 340 nm, 440 nm and 600 nm, and the best surface temperature of the catalytic material is 275 °C. The limits of detection of this method are 0.3 mg?m^?3 for trimethylamine, 0.07 mg?m^?3 for formaldehyde, and 0.2 mg?m^?3 for benzene. The linear ranges of CTL intensity versus gas/vapor concentration are from 1.0 to 65.1 mg?m^?3 for trimethylamine, from 0.2 to 72.5 mg?m^?3 for formaldehyde, and from 0.5 to 77.5 mg?m^?3 for benzene. The recoveries after testing 10 standard samples ranged from 98.1% to 102.6% for trimethylamine, from 98.1% to 102.6% for formaldehyde, and from 97.7% to 103.8% for benzene. Gaseous ammonia, acetaldehyde, toluene, ethylbenzene, ethanol, sulfur dioxide and carbon dioxide do not interfere. The relative deviation of the CTL signals after 200 h of continuous detection of trimethylamine, formaldehyde and benzene is <3%.

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Graphical abstract Schematic of a cataluminescence (CTL) based method for simultaneous determination of trimethylamine (TMA), formaldehyde (HCHO) and benzene (C₆H₆) in air. The linear ranges of CTL intensity versus gas/vapor concentration are from 1.0 to 65.1 mg?m^?3 for TMA, from 0.2 to 72.5 mg?m^?3 for HCHO, and from 0.5 to 77.5 mg?m^?3 for C₆H₆.

     

Sn-doped Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> cathode materials for lithium-ion batteries with enhanced electrochemical performance

Sn-doped Li-rich layered oxides of Li_1.2Mn_0.54-x Ni_0.13Co_0.13Sn _x O₂ have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn⁴⁺ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn⁴⁺, the electrochemical performance of Li_1.2Mn_0.54-x Ni_0.13Co_0.13Sn _x O₂ cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li_1.2Mn_0.53Ni_0.13Co_0.13Sn_0.01O₂ electrode delivers a high initial discharge capacity of 268.9 mAh g^?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g^?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li_1.2Mn_0.53Ni_0.13Co_0.13Sn_0.01O₂ electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g^?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g^?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn⁴⁺ for Mn⁴⁺ enlarges the Li⁺ diffusion channels due to its larger ionic radius compared to Mn⁴⁺ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode materials.     

LiMO<Subscript>2</Subscript>@Li<Subscript>2</Subscript>MnO<Subscript>3</Subscript> positive-electrode material for high energy density lithium ion batteries

Li[Ni_1/3Co_1/3Mn_1/3]O₂ (NCM 111) is a promising alternative to LiCoO₂, as it is less expensive, more structurally stable, and has better safety characteristics. However, its capacity of 155 mAh g^?1 is quite low, and cycling at potentials above 4.5 V leads to rapid capacity deterioration. Here, we report a successful synthesis of lithium-rich layered oxides (LLOs) with a core of LiMO₂ (R-3m, M?=?Ni, Co) and a shell of Li₂MnO₃ (C2/m) (the molar ratio of Ni, Co to Mn is the same as that in NCM 111). The core–shell structure of these LLOs was confirmed by XRD, TEM, and XPS. The Rietveld refinement data showed that these LLOs possess less Li⁺/Ni²⁺ cation disorder and stronger M*–O (M*?=?Mn, Co, Ni) bonds than NCM 111. The core–shell material Li_1.15Na_0.5(Ni_1/3Co_1/3)_core(Mn_1/3)_shellO₂ can be cycled to a high upper cutoff potential of 4.7 V, delivers a high discharge capacity of 218 mAh g^?1 at 20 mA g^?1, and retains 90 % of its discharge capacity at 100 mA g^?1 after 90 cycles; thus, the use of this material in lithium ion batteries could substantially increase their energy density.

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Graphical Abstract Average voltage vs. number of cycles for the core–shell and pristine materials at 20 mA g^?1 for 10 cycles followed by 90 cycles at 100 mA g^?1

     

Direct fabrication of anatase TiO<Subscript>2</Subscript> hollow microspheres for applications in photocatalytic hydrogen evolution and lithium storage

Hollow titanium dioxide (TiO₂) microspheres were synthesized in one step by employing tetrabutyl orthotitanate (TBOT) as a precursor through a facile solvothermal method in the presence of NH₄HCO₃. XRD analysis indicated that anatase TiO₂ can be obtained directly without further annealing. TiO₂ hollow microspheres with diameters in the range of 1.0–4.0 μm were confirmed through SEM and TEM measurements. The specific surface area was measured to be 180 m² g^?1 according to the nitrogen adsorption–desorption isotherms. Superior photocatalytic performance and good lithium storage properties were achieved for resultant TiO₂ samples. The H₂ evolution rate of the optimal sample is about 0.66 mmol h^?1 after loaded with 1 wt.% Pt (20 mg samples). The reversible capacity remained 143 mAh g^?1 at a specific current of 300 mA g^?1 after 100 charge–discharge cycles. This work provides a facile strategy for the preparation of hollow titanium dioxide microspheres and demonstrates their promising photocatalytic H₂ evolution and the lithium storage properties.

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Graphical abstract Hollow titanium dioxide spheres are directly synthesized via a facile template-free solvothermal method with the presence of NH₄HCO₃ based on inside-out Ostwald ripening (see picture), and demonstrated both as a photocatalyst for water splitting and a promising anode material for lithium-ion batteries. Superior photocatalytic performance and excellent lithium storage properties are achieved for resultant TiO₂ hollow microspheres.

     

Combined electrochemiluminescent and electrochemical immunoassay for interleukin 6 based on the use of TiO<Subscript>2</Subscript> mesocrystal nanoarchitectures

A dual-responsive sandwich-type immunosensor is described for the detection of interleukin 6 (IL-6) by combining electrochemiluminescent (ECL) and electrochemical (EC) detection based on the use of two kinds of TiO₂ mesocrystal nanoarchitectures. A composite was prepared from TiO₂ (anatase) mesocages (AMCs) and a carboxy-terminated ionic liquid (CTIL) and then placed on a glassy carbon electrode (GCE). In the next step, the ECL probe Ru(bpy)₃(II) and antibody against IL-6 (Ab₁) were immobilized on the GCE. Octahedral anatase TiO₂ mesocrystals (OAMs) served as the matrix for immobilizing acid phosphatase (ACP) and secondary antibody (Ab₂) labeled with horseradish peroxidase (HRP) to form a bioconjugate of type Ab₂-HRP/ACP/OAMs. It was self-assembled on the GCE by immunobinding. 1-Naphthol, which is produced in-situ on the surface of the GCE due to the hydrolysis of added 1-naphthyl phosphate by ACP, is oxidized by HRP in the presence of added H₂O₂. This results in an electrochemical signal (typically measured at 0.4 V vs. Ag/AgCl) that increases linearly in the 10 fg·mL^?1 to 90 ng·mL^?1 IL-6 concentration range with a detection limit of 0.32 fg·mL^?1. Secondly, the oxidation product of 1-naphthol quenches the ECL emission of Ru(bpy)₃²⁺. This leads to a decrease in ECL intensity which is linear in the 10 ag·mL^?1 to 90 ng·mL^?1 concentration range, with a detection limit of 3.5 ag·mL^?1. The method exhibits satisfying selectivity and good reproducibility which demonstrates its potential in clinical testing and diagnosis.

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Graphical abstract A dual-responsive sandwich-type immunosensor was fabricated for the detection of interleukin 6 by combining electrochemiluminescence and electrochemical detection based on the use of two kinds of TiO₂ mesocrystal nanoarchitectures.