Suping Jia

Nitrogen-doped hollow carbon nanoparticles as efficient counter electrodes in quantum dot sensitized solar cells

The functions of nitrogen-doped hollow carbon nanoparticles (N-HCNPs) as counter electrodes in quantum dot sensitized solar cells (QDSSCs) have been studied in this paper. Electrochemical impedance spectroscopy (EIS) and Tafel-polarization tests reveal a low charge transfer resistance and a high exchange current density between polysulfide electrolyte and the N-HCNPs electrode. Cyclic voltammetry results indicate that the N-HCNPs electrode shows high electrocatalytic activity and excellent tolerance toward the S 2� /Sn 2� electrolyte. A power conversion efficiency of 2.67% is achieved for the QDSSCs based on N-HCNPs counter electrodes, which is clearly higher than those of the QDSSCs based on HCNPs, carbon nanotubes and Pt counter electrodes. The results reveal that the N-HCNPs electrode is a promising counter electrode candidate for QDSSCs.

Photoelectrochemical detection of oxidative DNA damage induced by Fenton reaction with low concentration and DNA-associated Fe2+.

The metal ion dependent decomposition of hydrogen peroxide, the so-called Fenton Reaction, yields hydroxyl radicals that can cause oxidative DNA damage both in vitro and in vivo. We have previously reported a photoelectrochemical sensor for the detection of oxidative DNA damage induced by an Fe(2+)-mediated Fenton Reaction, using a DNA intercalator as a photoelectrochemical signal reporter (Liang, M.; Guo, L.-H. Environ. Sci. Technol. 2007, 41, 658). The intercalator binds less to the damaged DNA in the sensor film than the native form, resulting in a reduction in the measured photocurrent. In this report, some mechanistic aspects of the sensor were investigated. It was found that Fe(2+) alone (without the coexistence of H(2)O(2)) suppressed the photocurrent of the intercalator bound to the DNA film in a pH-dependent manner. Similar pH dependence was observed for the zeta potential of the tin oxide nanoparticle colloid used in the preparation of the semiconductor electrode, leading to the hypothesis that the metal ion binds to the surface oxide groups on the electrode and quenches the photoelectrochemical response. At pH 3, the quenching effect was reduced substantially to permit the detection of DNA damage by as low as 10 muM Fe(2+) and 40 microM H(2)O(2), a concentration that is within the physiologically relevant range. It was also found that Fe2+ ions associated with the DNA in the sensor film and participated in the DNA damage reaction, a mechanism that has been implicated in previous studies on metal carcinogenesis.

Graphene Frameworks Promoted Electron Transport in Quantum Dot-Sensitized Solar Cells

Graphene frameworks (GFs) were incorporated into TiO2 photoanode as electron transport medium to improve the photovoltaic performance of quantum dot-sensitized solar cells (QDSSCs) for their excellent conductivity and isotropic framework structure that could permit rapid charge transport. Intensity modulated photocurrent/photovoltage spectroscopy and electrochemical impedance spectroscopy results show that the electron transport time (τ(d)) of 1.5 wt % GFs/TiO2 electrode is one-fifth of that of the TiO2 electrode, and electron lifetime (τ(n)) and diffusion path length (Ln) are thrice those of the TiO2 electrode. Results also revealed that the GFs/TiO2 electrode has a shorter electron transport time (τ(d)), as well as longer electron lifetime (τ(n)) and diffusion path length (Ln), than conventional 2D graphene sheets/TiO2 electrode, thus indicating that GFs could promote rapid electron transfer in TiO2 photoanodes. Photocurrent-voltage curves demonstrated that when incorporating 1.5 wt % GFs into TiO2 photoanode, a maximum power conversion efficiency of 4.2% for QDSSCs could be achieved. This value was higher than that of TiO2 photoanode and 2D graphene sheets/TiO2 electrode. In addition, the reasons behind the sensitivity of photoelectric conversion efficiency to the graphene concentration in the TiO2 were also systematically investigated. Our results provide a basic understanding of how GFs can efficiently promote electron transport in TiO2-based solar cells.

Synthesis and electrocatalytic performance of nitrogen-doped macroporous carbons

Nitrogen-doped carbons with highly ordered macroporous structures are fabricated via the assembly and carbonization of polymethylmethacrylate (PMMA)–polyacrylonitrile (PAN) core–shell nanoparticles. During the carbonization, PMMA (acting as a template) is completely removed, and the resulting hollow PAN particles are fused to form ordered macroporous structures. Micropores are present on the macropore walls, providing desirable inter-macropore channels. The nitrogen atoms partially remain in the resulting carbon structures and exhibit mainly pyridinic and quaternary configurations under relatively high carbonization temperatures. The careful control of the pre-stabilization and carbonization conditions is crucially important for the formation of the ordered macroporous structures. As a demonstration, the obtained nitrogen-doped macroporous carbons exhibit excellent electrochemical catalytic activities both for the reduction of Sn2− electrolyte ions in QDSSCs and the reduction of oxygen in fuel cells.

Tunneling Interlayer for Efficient Transport of Charges in Metal Oxide Electrodes

Due to the limited electronic conductivity, the application of many metal oxides that may have attractive (photo)-electrochemical properties has been limited. Regarding these issues, incorporating low-dimensional conducting scaffolds into the electrodes or supporting the metal oxides onto the conducting networks are common approaches. However, some key electronic processes like interfacial charge transfer are far from being consciously concerned. Here we use a carbon-TiO2 contact as a model system to demonstrate the electronic processes occurring at the metal-semiconductor interface. To minimize the energy dissipation for fast transfer of electrons from semiconductor to carbon scaffolds, facilitating electron tunneling while avoiding high energy-consuming thermionic emission is desired, according to our theoretical simulation of the voltammetric behaviors. To validate this, we manage to sandwich ultrathin TiO2 interlayers with heavy electronic doping between the carbon conductors and dopant-free TiO2. The radially graded distribution of the electronic doping along the cross-sectional direction of carbon conductor realized by immobilizing the dopant species on the carbon surface can minimize the energy consumption for contacts to both the carbon and the dopant-free TiO2. Our strategy provides an important requirement for metal oxide electrode design.

Chlorine-Induced In Situ Regulation to Synthesize Graphene Frameworks with Large Specific Area for Excellent Supercapacitor Performance

Three-dimensional (3D) graphene frameworks are usually limited by a complicated preparation process and a low specific surface area. This paper presents a facile suitable approach to effectively synthesize 3D graphene frameworks (GFs) with large specific surface area (up to 1018 m(2) g(-1)) through quick thermal decomposition from sodium chloroacetate, which are considerably larger than those of sodium acetate reported in our recent study. The chlorine element in sodium chloroacetate may possess a strong capability to induce in situ activation and regulate graphene formation during pyrolysis in one step. These GFs can be applied as excellent electrode materials for supercapacitors and can achieve an enhanced supercapacitor performance with a specific capacitance of 266 F g(-1) at a current density of 0.5 A g(-1).

Highly efficient visible light-driven hydrogen production of precious metal-free hybrid photocatalyst: CdS@NiMoS core–shell nanorods

Well-shaped precious metal-free hybrid photocatalysts with low cost and high efficiency of photocatalytic H2 evolution are of great significance for clean energy. Herein, we report that NiMoS, a non-noble metal co-catalyst used for forming a well-designed one-dimensional (1D) CdS@NiMoS core–shell nanorod photocatalyst system, greatly improves the efficiency and durability for photogeneration of hydrogen in water. The intimate interaction between the CdS nanorod core and the NiMoS thin shell enhances the separation of the photogenerated electron–hole pair, and the large contact surface area improves the utilization efficiency of the photogenerated electrons. Consequently, the optimal loading content of NiMoS is 3 wt% for CdS, giving a photocatalytic H2 production rate of 185.4 mmol g−1 h−1, which is about 16.55, 5.24 and 3.85 times higher than that of 2 wt% Pt/CdS, 3 wt% CdS@MoS2 and 3 wt% CdS@NiS, respectively, and the apparent quantum efficiency at 420 nm over CdS@NiMoS reaches 21.82%. This study provides a simple method for constructing high performance and low cost photocatalysts, which enhance photocatalytic H2 evolution.

Kinetic reconstruction of TiO2 surfaces as visible-light-active crystalline phases with high photocatalytic performance

Modulation of the TiO2 structure to achieve efficient photocatalytic usage of solar light is still a challenging issue. Here we report that simple bombardment of anatase TiO2 nanocrystals by hot molecules can alter its phase transformation kinetics and lead to the reconstruction of the resulting rutile surfaces into a metastable TiO2 crystalline structure. Moreover, the metastable surface crystalline phase is able to harvest visible light up to 480 nm, and exhibits good properties for photocurrent generation. Photocatalysis tests show that upon irradiation by visible light (λ > 420 nm), the surface-reconstructed TiO2 crystals display excellent and stable photocatalytic activity for hydrogen production from aqueous ethanol solution, with a hydrogen production rate of 302 μmol g−1 h−1. This finding might bring a new approach to kinetically tune the structure of TiO2 or other semiconductor crystals in order to modulate their properties.

Structure-controlled CdS(0D, 1D, 2D) embedded onto 2D ZnS porous nanosheets for highly efficient photocatalytic hydrogen generation

The morphological characteristics of a photocatalyst is central to its photocatalytic activity for solar energy conversion. Herein, Pt–ZnS/CdS composites comprising ZnS nanosheets, embedded via the geometry and size modulation and tuning of band gap of CdS with 0D, 1D or 2D structure, were investigated for solar hydrogen production. The photoactivity results indicate that the shape and morphology of CdS in the Pt–ZnS/CdS heterojunction play a pivotal role in affecting the photocatalytic performance. CdS with a 1D structure deposited on porous Pt–ZnS nanosheets endow the heterojunction with increased efficiency for the separation and transport of photoinduced electron–hole pairs. The proposed mechanism for the boosted suppression of charge recombination was further confirmed by the transient photocurrent response and photoluminescence.

Direct C–C coupling of bio-ethanol into 2,3-butanediol by photochemical and photocatalytic oxidation with hydrogen peroxide

Theoretically, selective C–H manipulation in ethanol can result in a direct C–C coupling synthesis of 2,3-butanediol (2,3-BDO). However, this process is typically extremely difficult to achieve because of the high complexity of the involved chemical bonds. In this work, we determine that hydroxide radicals generated from the photolysis of H2O2 can selectively attack the α-hydrogen atom in ethanol aqueous solutions and crack the C–H bond to produce hydroxyethyl radicals, which subsequently undergo C–C coupling to form 2,3-BDO. This selective C–H breakage is determined by the reaction rate, which is primarily controlled by the local H2O2 concentration at a given irradiation intensity. At a moderate reaction rate of ethanol (37 mmol h−1), the 2,3-BDO selectivity reaching as high as 91% can be obtained. The introduction of a catalyst can further increase ethanol conversion and enhance the 2,3-BDO formation rate by controlling the reaction rate. This result provides an environment-friendly approach to convert bio-ethanol directly to 2,3-BDO and to manipulate a single bond selectively in complex bonding situations.