Ion concentration polarization near microchannel-nanochannel interfaces: effect of pH value

This study investigates the effect of the pH value on the ion concentration polarization phenomenon and the nonlinear current-voltage characteristics of a hybrid soda-lime glass micro/nanochannel for a constant KCl salt concentration of about 1 mM. The experimental results show that the electrical conductance of the nanochannel in the Ohmic regime and the critical threshold voltage of the limiting current are both dependent on the pH value of the salt solution when the electrical double layer thickness is considerable in the nanochannel. Specifically, the nanochannel conductance increases and the critical threshold voltage for the limiting current decreases as the pH value is increased. It also suggests that a higher pH value induces a higher surface charge density on the nanochannel walls, and therefore increases both the ionic conductance and the counter-ion flux within the nanochannel.     

Evaluating the Free Energies of Solvation and Electronic Structures of Lithium‐Ion Battery Electrolytes

Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li⁺ with pure carbonates and ethylene carbonate (EC)‐based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06‐2X/6‐311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li‐ion solvation in carbonates and EC‐based mixtures. A strong local tetrahedral order involving four carbonates around the Li⁺ was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li⁺ ion with carbonates are negative and suggested the ion–carbonate complexation process to be exothermic and spontaneous. Natural bond orbital analysis indicated that Li⁺ interacts with the lone pairs of electrons on the carbonyl oxygen atom in the primary solvation sphere. These interactions lead to an increase in the carbonyl (C=O) bond lengths, as evidenced by a redshift in the vibrational frequencies [ν(C=O)] and a decrease in the electron density values at the C=O bond critical points in the primary solvation sphere. Quantum theory of atoms in molecules, localized molecular orbital energy decomposition analysis (LMO‐EDA), and noncovalent interaction plots revealed the electrostatic nature of the Li⁺ ion interactions with the carbonyl oxygen atoms in these complexes. On the basis of LMO‐EDA, the strongest attractive interaction in these complexes was found to be the electrostatic interaction followed by polarization, dispersion, and exchange interactions. Overall, our calculations predicted EC and a binary mixture of EC/dimethyl carbonate to be appropriate electrolytes for Li‐ion batteries, which complies with experiments and other theoretical results.     

Estimation and Comparison of Pore Charge on Titania and Zirconia Membranes Prepared by Sol-Gel Route Using Zeta Potential Measurement

An attempt has been made to synthesize ceramic titania and zirconia membranes by sol-gel process by filtering respective viscous colloidal sol through microporous alumina support and gelling followed by sintering at 400°C and 470°C respectively. The static charge on the pores of the so formed membranes and the pore size distribution determine the applicability in filtering colloidal solution. The mean pore size from SEM were found to be 0.65 m and 0.54 m for titania and zirconia membranes respectively with 1.47 × 10⁷/cm² as pore density for both. The filtration characteristics during membrane layer formation showed that the membrane layer formation started after 35 minutes in the case of titania membrane and 40 minutes in the case of zirconia membrane. From the gravimetric estimation of water content of the membranes the thickness of the membrane was found out to be 3 m and the porosity was found out to be 0.30 for both the cases. The particle charge density was estimated from the zeta potential and the particle size. The pore charge density was estimated from the particle charge density, pore density, pore diameter and the thickness of the membrane layer. The membrane pore charge density was found to vary between 3 to –1 Coulombs/cm² in the case of titania membrane and 7 to –0.5 Coulombs/cm² in the case of zirconia membrane in the pH range 1–12.     

压力对带有pH值可调聚电解质刷的仿生纳米孔中离子选择性的影响

具有pH值可调聚电解质（Polyelectrolyte,PE）刷的合成纳米孔的仿生离子通道在纳米尺度下离子、流体和生物粒子的主动运输控制方面具有重大应用潜力. 离子选择性是纳流体设备中离子传输的重要现象,具有很大的现实意义和实用价值. 本文提出了施加压力控制纳米孔中离子选择度的方法,综合研究了溶液pH值、浓度、外加电压和压力对离子选择度的影响. 仿真结果表明,离子选择度对压力的刺激是敏感的,且不像电压对离子选择度的影响会受到溶液pH值和浓度的制约,且方向不定,速度不可控;压力对离子选择度的影响不受溶液性质制约,并且灵活可控. 该结果对设计带pH值可调聚电解质刷的纳米孔有重要的启发作用.     

Ultrafast Preparation of Monodisperse Fe3O4 Nanoparticles by Microwave‐Assisted Thermal Decomposition

Thermal decomposition, as the main synthetic procedure for the synthesis of magnetic nanoparticles (NPs), is facing several problems, such as high reaction temperatures and time consumption. An improved a microwave‐assisted thermal decomposition procedure has been developed by which monodisperse Fe₃O₄ NPs could be rapidly produced at a low aging temperature with high yield (90.1 %). The as‐synthesized NPs show excellent inductive heating and MRI properties in vitro. In contrast, Fe₃O₄ NPs synthesized by classical thermal decomposition were obtained in very low yield (20.3 %) with an overall poor quality. It was found for the first time that, besides precursors and solvents, magnetic NPs themselves could be heated by microwave irradiation during the synthetic process. These findings were demonstrated by a series of microwave‐heating experiments, Raman spectroscopy and vector‐network analysis, indicating that the initially formed magnetic Fe₃O₄ particles were able to transform microwave energy into heat directly and, thus, contribute to the nanoparticle growth.     

Photoinduced energy transfer and charge transfer on squarylium cyanine dyes

A series of squarylium cyanine dyes (Sqs) were synthesized to explore their applications in functional devices.Preliminary investigation on the mechanism involved in these devices was carried out.Spectroscopic behavior of Sqs with porphyrin (P),8-hydroxyquinolium aluminum (Alq) and ruthenium bipyridyl complex (Ru(bipy)) in solution,in film and on nanocrystalline TiO2 was investigated,respectively.A mechanism including photoinduced energy transfer and charge transfer processes was suggested in the corresponding practical devices.By means of doping,a red organic electroluminescent device (ELD) using Sq-doped Alq as the emission layer (EML) has been developed,and the total light to electricity efficiency of nanocrystalline TiO2 electrode based on using Sq-doped Ru(bipy) as photosensitizer has been improved greatly in the whole visible region,particularly in the red area above 600 nm.     

Novel carboxylated oligothiophenes as sensitizers in photoelectric conversion systems

Novel carboxylated oligothiophenes with different thiophene units were designed and synthesized as photosensitizers in dye-sensitized solar cells (DSSCs) for efficient opto-electric materials. The introduction of -COOH into thiophene molecules can lead to a red shift of UV-visible absorption, increase light-harvesting efficiency, and enhance photoinduced charge transport by forming efficient covalent bonds to the substrate surface. A red shift of the absorption spectrum of oligothiophene is also achieved by the increase in the number of thiophene units. The DSSCs based on the oligomers have excellent photovoltaic performances. Under 100 mW cm(-2) irradiation a short-circuit current of 10.57 mA cm(-2) and an overall energy conversion efficiency of 3.36 % is achieved when pentathiophene dicarboxylated acid was used as a sensitizer. The incident photo-to-current conversion efficiency (IPCE) has a maximum as high as 80 %. In addition, photovoltage and photocurrent transients show that slow charge recombination in DSSCs is important for efficient charge separation and excellent photoelectric conversion properties of the oligomers. These initial and promising results suggest that carboxylated oligothiophenes are efficient photosensitizers.     

Platinum Alloy Tailored All‐Weather Solar Cells for Energy Harvesting from Sun and Rain

Solar cells that can harvest energy in all weathers are promising in solving the energy crisis and environmental problems. The power outputs are nearly zero under dark conditions for state‐of‐the‐art solar cells. To address this issue, we present herein a class of platinum alloy (PtM_x, M=Ni, Fe, Co, Cu, Mo) tailored all‐weather solar cells that can harvest energy from rain and realize photoelectric conversion under sun illumination. By tuning the stoichiometric Pt/M ratio and M species, the optimized solar cell yields a photoelectric conversion efficiency of 10.38 % under simulated sunlight irradiation (AM 1.5, 100 mW cm^?2) as well as current of 3.90 μA and voltage of 115.52 μV under simulated raindrops. Moreover, the electric signals are highly dependent on the dripping velocity and the concentration of simulated raindrops along with concentrations of cation and anion.     

Traps for charge carriers in molecular materials formed by dipolar species: towards light-driven molecular switch

The influence of polar species on the transport and trapping of charge carriers is discussed. Calculations performed on a model molecular lattice demonstrate that polar dopants locally modify the polarization energy thus creating traps for charge carriers in the vicinity of the dipole. The presence of polar dopants in disordered solids gives rise to a broadening of the density-of-states function. A scheme of a molecular switch has been put forward, based on electrostatic interactions between photochromic moieties and charge carriers travelling on a molecular wire (conjugated polymer chain).     

Integration of Semiconducting Sulfides for Full‐Spectrum Solar Energy Absorption and Efficient Charge Separation

The full harvest of solar energy by semiconductors requires a material that simultaneously absorbs across the whole solar spectrum and collects photogenerated electrons and holes separately. The stepwise integration of three semiconducting sulfides, namely ZnS, CdS, and Cu_2?xS, into a single nanocrystal, led to a unique ternary multi‐node sheath ZnS–CdS–Cu_2?xS heteronanorod for full‐spectrum solar energy absorption. Localized surface plasmon resonance (LSPR) in the nonstoichiometric copper sulfide nanostructures enables effective NIR absorption. More significantly, the construction of pn heterojunctions between Cu_2?xS and CdS leads to staggered gaps, as confirmed by first‐principles simulations. This band alignment causes effective electron–hole separation in the ternary system and hence enables efficient solar energy conversion.     

Tuning the HOMO energy levels of organic dyes for dye-sensitized solar cells based on Br-/Br3- electrolytes

A series of novel metal-free organic dyes TC301-TC310 with relatively high HOMO levels were synthesized and applied in dye-sensitized solar cells (DSCs) based on electrolytes that contain Br(-)/Br(3)(-) and I(-)/I(3)(-). The effects of additive Li(+) ions and the HOMO levels of the dyes have an important influence on properties of the dyes and performance of DSCs. The addition of Li(+) ions in electrolytes can broaden the absorption spectra of the dyes on TiO(2) films and shift both the LUMO levels of the dyes and the conduction band of TiO(2), thus leading to the increase of J(sc) and the decrease of V(oc). Upon using Br(-)/Br(3)(-) instead of I(-)/I(3)(-), a large increase of V(oc) is attributed to the enlarged energy difference between the redox potentials of electrolyte and the Fermi level of TiO(2), as well as the suppressed electron recombination. Incident photon to current efficiency (IPCE) action spectra, electrochemical impedance spectra, and nanosecond laser transient absorption reveal that both the electron collection yields and the dye regeneration yields (Φ(r)) depend on the potential difference (the driving forces) between the oxidized dyes and the Br(-)/Br(3)(-) redox couple. For the dyes for which the HOMO levels are more positive than the redox potential of Br(-)/Br(3)(-) sufficient driving forces lead to the longer effective electron-diffusion lengths and almost the same efficient dye regenerations, whereas for the dyes for which the HOMO levels are similar to the redox potential of Br(-)/Br(3)(-), insufficient driving forces lead to shorter effective electron-diffusion lengths and inefficient dye regenerations.     

Ge‐Mediated Modification in Ta3N5 Photoelectrodes with Enhanced Charge Transport for Solar Water Splitting

Ta₃N₅ is a promising photoanode candidate for photoelectrochemical water splitting, with a band gap of about 2.1 eV and a theoretical solar‐to‐hydrogen efficiency as high as 15.9 % under AM 1.5 G 100 mW cm^?2 irradiation. However, the presently achieved highest photocurrent (ca. 7.5 mA cm^?2) on Ta₃N₅ photoelectrodes under AM 1.5 G 100 mW cm^?2 is far from the theoretical maximum (ca. 12.9 mA cm^?2), which is possibly due to serious bulk recombination (poor bulk charge transport and charge separation) in Ta₃N₅ photoelectrodes. In this study, we show that volatilization of intentionally added Ge (5 %) during the synthesis of Ta₃N₅ promotes the electron transport and thereby improves the charge‐separation efficiency in bulk Ta₃N₅ photoanode, which affords a 320 % increase of the highest photocurrent comparing with that of pure Ta₃N₅ photoanode under AM 1.5 G 100 mW cm^?2 simulated sunlight.     

Photosynthetic Antenna–Reaction Center Mimicry by Using Boron Dipyrromethene Sensitizers

Various molecular and supramolecular systems have been synthesized and characterized recently to mimic the functions of photosynthesis, in which solar energy conversion is achieved. Artificial photosynthesis consists of light‐harvesting and charge‐separation processes together with catalytic units of water oxidation and reduction. Among the organic molecules, derivatives of BF₂‐chelated dipyrromethene (BODIPY), “porphyrin’s little sister”, have been widely used in constructing these artificial photosynthetic models due to their unique properties. In these photosynthetic models, BODIPYs act as not only excellent antenna molecules, but also as electron‐donor and ‐acceptor molecules in both the covalently linked molecular and supramolecular systems formed by axial coordination, hydrogen bonding, or crown ether complexation. The relationships between the structures and photochemical reactivities of these novel molecular and supramolecular systems are discussed in relation to the efficiency of charge separation and charge recombination. Femto‐ and nanosecond transient absorption and photoelectrochemical techniques have been employed in these studies to give clear evidence for the occurrence of energy‐ and electron‐transfer reactions and to determine their rates and efficiencies.