Defective Potassium Poly(Heptazine Imide) Preventing Spin Delocalization and Hole Transfer Deactivation for Efficient Solar Energy Conversion and Storage.

Anti-site defective potassium poly(heptazine imide) (KPHI) with the central nitrogen atoms partially replaced by graphitic carbon atoms in the flawed heptazine rings is prepared by direct ionothermal treatment of the rationally designed supramolecular complex in KSCN salt molten. Compared to the KPHIs without the anti-site defect, the anti-site defective KPHI demonstrates significantly improved photocatalytic and dark photocatalytic performances for H2 evolution reaction (HER). In the presence of the hole scavenger, the anti-site defective KPHI exhibits superior photocatalytic stability for HER lasting 20 h, whereas the deactivation is observed from the ordinary KHPIs after 3 h HER. Moreover, the H2 yield in the dark by the stored photoelectrons in the anti-site defective KPHI increases by more than an order of magnitude. Density functional theory calculations reveal that the anti-site defective unit in KPHI not only prevents spin delocalization but also inhibits the deactivation of hole transfer, which are beneficial to photoelectron storage and photocatalytic activity. The findings in this study provide insight into the photophysical and catalytic properties of KPHI, which conclude a strategy to improve the performances for solar energy conversion and storage by incorporating intrinsic anti-site defects in KPHI.

Ionization of Volatile Organics and Nonvolatile Biomolecules Directly from a Titanium Slab for Mass Spectrometric Analysis.

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) and electrospray ionization (ESI)-MS can cover the analysis of analytes from low to high polarities. Thus, an ion source that possesses these two ionization functions is useful. Atmospheric surface-assisted ionization (ASAI), which can be used to ionize polar and nonpolar analytes in vapor, liquid, and solid forms, was demonstrated in this study. The ionization of analytes through APCI or ESI was induced from the surface of a metal substrate such as a titanium slab. ASAI is a contactless approach operated at atmospheric pressure. No electric contacts nor any voltages were required to be applied on the metal substrate during ionization. When placing samples with high vapor pressure in condensed phase underneath a titanium slab close to the inlet of the mass spectrometer, analytes can be readily ionized and detected by the mass spectrometer. Furthermore, a sample droplet (~2 µL) containing high-polarity analytes, including polar organics and biomolecules, was ionized using the titanium slab. One titanium slab is sufficient to induce the ionization of analytes occurring in front of a mass spectrometer applied with a high voltage. Moreover, this ionization method can be used to detect high volatile or polar analytes through APCI-like or ESI-like processes, respectively.

Role of Interfacial Defects in Photoelectrochemical Properties of BiVO4 Coated on ZnO Nanodendrites: X-ray Spectroscopic and Microscopic Investigation.

Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core-shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core-shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p-V 3d hybridization and reduce the crystal field energy 10Dq ∼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron-hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron-hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core-shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.

Efficacious CO2 Photoconversion to C2 and C3 Hydrocarbons on Upright SnS-SnS2 Heterojunction Nanosheet Frameworks.

In this work, SnS-SnS2 heterostructured upright nanosheet frameworks are constructed on FTO substrates, which demonstrate promising photocatalytic performances for the conversion of CO2 and water to C2 (acetaldehyde) and C3 (acetone) hydrocarbons without H2 formation. With post annealing in designated atmospheres, the photocatalytic activity of the SnS-SnS2 heterostructured nanosheet framework is critically enhanced by increasing the fraction of crystalline SnS in nanosheets through partial transformation of the SnS2 matrix to SnS but not obviously influenced by improving the crystallinity of the SnS2 matrix. DFT calculations indicate that transformed SnS possesses the CO2 adsorption sites with significantly lower activation energy for the rate-determining step to drive efficient CO2 conversion catalysis. The experimental results and DFT calculations suggest that the SnS-SnS2 heterojunction nanosheet framework photocatalyst experiences Z-scheme charge transfer dynamic to allow the water oxidation and CO2 reduction reactions occurring on the surfaces of SnS2 and SnS, respectively. The Z-scheme SnS-SnS2 heterostructured nanosheet framework photocatalyst exhibits not only efficient charge separation but also highly catalytic active sites to boost the photocatalytic activity for CO2 conversion to C2 and C3 hydrocarbons.

Microscopic Revelation of Charge-Trapping Sites in Polymeric Carbon Nitrides for Enhanced Photocatalytic Activity by Correlating with Chemical and Electronic Structures.

The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.

Toward Eco-Friendly and Highly Efficient Solar Water Splitting Using In2S3/Anatase/Rutile TiO2 Dual-Staggered-Heterojunction Nanodendrite Array Photoanode.

The TiO2-based heterojunction nanodendrite (ND) array composed of anatase nanoparticles (ANPs) on the surface of the rutile ND (RND) array is selected as the model photoanode to demonstrate the strategies toward eco-friendly and efficient solar water splitting using neutral electrolyte and seawater. Compared with the performances in alkaline electrolyte, a non-negligible potential drop across the electrolyte as well as impeded charge injection and charge separation is monitored in the ANP/RND array photoanode with neutral electrolyte, which are, respectively, ascribed to the series resistance of neutral electrolyte, the fundamentally pH-dependent water oxidation mechanism on TiO2 surface, as well as the less band bending at the interface of TiO2 and neutral electrolyte. Accordingly, a TiO2-based dual-staggered heterojunction ND array photoanode is further designed in this work to overcome the issue of less band bending with the neutral electrolyte. The improvement of charge separation efficiency is realized by the deposition of a transparent In2S3 layer on the ANP/RND array photoanode for constructing additional staggered heterojunction. Under illumination of AM 1.5G (100 mW cm-2), the improved photocurrent densities acquired both in neutral electrolyte and seawater at 1.23 V vs reversible hydrogen electrode (RHE), which approach the theoretical value for rutile TiO2, are demonstrated in the dual-staggered-heterojunction ND array photoanode. Faradaic efficiencies of ∼95 and ∼32% for solar water oxidation in neutral electrolyte and solar seawater oxidation for 2 h are acquired at 1.23 V vs RHE, respectively.

Porphyrin Dye-Sensitized Zinc Oxide Aggregated Anodes for Use in Solar Cells.

Porphyrin YD2-o-C8-based dyes were employed to sensitize room-temperature (RT) chemical-assembled ZnO aggregated anodes for use in dye-sensitized solar cells (DSSCs). To reduce the acidity of the YD2-o-C8 dye solution, the proton in the carboxyl group of a porphyrin dye was replaced with tetrabuthyl ammonium (TBA⁺) in this work. The short-circuit current density (Jsc) of the YD2-o-C8-TBA-sensitized ZnO DSSCs is higher than that of the YD2-o-C8-sensitized cells, resulting in the improvement of the efficiency of the YD2-o-C8-based ZnO DSSCs. With an appropriate incorporation of chenodeoxycholic acid (CDCA) as coadsorbate, the Jsc and efficiency of the YD2-o-C8-TBA-sensitized ZnO DSSC are enhanced due to the improvement of the incident-photon-to-current efficiency (IPCE) values in the wavelength range of 400-450 nm. Moreover, a considerable increase in Jsc is achieved by the addition of a light scattering layer in the YD2-o-C8-TBA-sensitized ZnO photoanodes. Significant IPCE enhancement in the range 475-600 nm is not attainable by tuning the YD2-o-C8-TBA sensitization processes for the anodes without light scattering layers. Using the RT chemical-assembled ZnO aggregated anode with a light scattering layer, an efficiency of 3.43% was achieved in the YD2-o-C8-TBA-sensitized ZnO DSSC.

Fabrication of an Efficient BiVO4-TiO2 Heterojunction Photoanode for Photoelectrochemical Water Oxidation.

In this work, a simple planar BiVO4/TiO2 heterojunction photoanode was prepared on a fluorine-doped tin oxide (FTO) substrate for photoelectrochemical (PEC) water oxidation. The measurements of surface photovoltage, photocurrent transient behavior, and hole-scavenger-assisted PEC performance indicate that charge separation efficiency is improved compared to that of the BiVO4/FTO photoanode. This improvement is caused by the formation of the staggered BiVO4/TiO2 heterojunction. However, the photocurrent densities of the BiVO4/TiO2/FTO photoanode are higher than those of the BiVO4/FTO one only at potentials >1.2 V vs reversible hydrogen electrode, although the two BiVO4 layers with comparable light harvesting efficiencies were prepared by the same method. The hole-scavenger-assisted PEC measurements reveal that the hole injection efficiency of the BiVO4/TiO2/FTO photoanode is inferior to that of the bare BiVO4/FTO anode for oxygen evolution. It shows that the surface property of the BiVO4 layers is altered as they are deposited on different substrates. On the basis of these characterizations, the cocatalyst cobalt phosphate (Co-Pi) was further deposited on the surface of BiVO4/TiO2/FTO photoanode to improve the hole injection efficiency. Subsequently, the photocurrent density and stability of the Co-Pi/BiVO4/TiO2/FTO photoanode were significantly improved compared to those of the bare BiVO4/FTO photoanode.

Charge collection enhancement by incorporation of gold-silica core-shell nanoparticles into P3HT:PCBM/ZnO nanorod array hybrid solar cells.

In this work, gold-silica core-shell (Au@silica) nanoparticles (NPs) with various silica-shell thicknesses are incorporated into P3HT:PCBM/ZnO nanorod (NR) hybrid solar cells. Enhancement in the short-circuit current density and the efficiency of the hybrid solar cells is attained with the appropriate addition of Au@silica NPs regardless of the silica-shell thickness. Compared to the P3HT:PCBM/ZnO NR hybrid solar cell, a 63% enhancement in the efficiency is achieved by the P3HT:PCBM/Au@silica NP/ZnO NR hybrid solar cell. The finite difference time domain simulations indicate that the strength of the Fano resonance, i.e., the electric field of the quasi-static asymmetric quadrupole, on the surface of Au@silica NPs in the P3HT:PCBM/ZnO NR hybrid significantly decreases with increasing thickness of the silica shell. Raman characterization reveals that the degree of P3HT order increases when Au@silica NPs are incorporated into the P3HT:PCBM/ZnO NR hybrid. The charge separation at the interface between P3HT and PCBM as well as the electron transport in the active layer are retarded by the electric field of the Fano resonance. Nevertheless, the prolongation of the electron lifetime and the reduction of the electron transit time in the P3HT:PCBM/ZnO NR hybrid solar cells, which result in an enhancement of electron collection, are achieved by the addition of Au@silica NPs. This may be attributed to the improvement in the degree of P3HT order and connectivity of PCBM when Au@silica NPs are incorporated into the P3HT:PCBM active layer.

n-Fe2O3 to N⁺-TiO2Heterojunction Photoanode for Photoelectrochemical Water Oxidation.

To improve the performance of the thin hematite photoanode for photoelectrochemical water oxidation, in this work, an nN(+) α-Fe2O3 (hematite)-TiO2 heterojunction photoanode is constructed on fluorine-doped tin oxide substrate to establish a built-in field in the space charge region for facilitating the charge separation in the hematite layer. Charge distribution in the hematite-TiO2 heterostructure is investigated using Kelvin probe force microscopy, which confirms the improvement of charge separation in hematite layer by the formation of energy-matched nN(+) α-Fe2O3-TiO2 heterojunction. Compared to the hematite photoanode, an eightfold enhancement of the photocurrent density at 1.23 V versus reversible hydrogen electrode is measured in the hematite-TiO2 heterojunction photoanode. By using hydrogen peroxide as a hole scavenger, it demonstrates that both charge separation and charge injection efficiencies in the hematite-TiO2 heterojunction photoanode are superior to those in the hematite photoanode. It results from the significant suppressions of the charge recombinations occurring within the hematite layer as well as at the interface of photoelectrode and electrolyte by the formation of the nN(+) α-Fe2O3-TiO2 heterojunction.

Photoreduction of graphene oxide enhanced by sacrificial agents.

In this work, the photoreduction of graphene oxides (GOs) was carried out in the presence of a sacrificial agent of Na2S/Na2SO3 and triethanolamine (TEA) separately in the solution. The photoreduction of GOs was enhanced with the addition of the sacrificial agent, which was examined in terms of reduction extent and needed reduction period. The quench of the GO emission was observed in the photoluminescence spectra of both GO solutions with Na2S/Na2SO3 and TEA. Although both sacrificial agents facilitated the charge transfer in the irradiated GO solutions, the aggregation of GO/reduced GO (RGO) occurred in the Na2S/Na2SO3-contained solution during photoreduction, which limited further photoreduction of GOs with the assistance of Na2S/Na2SO3. By keeping good dispersion characteristic during the whole process, the photoreduction efficiency of GO in the presence of TEA was therefore superior to that with the assistance of Na2S/Na2SO3.

P3HT-based nanoarchitectural Fano solar cells.

The finite difference time domain simulation shows the existence of an asymmetric quadrupole of Fano resonance on the surface of a gold-silica core-shell (Au@silica) nanoparticle (NP) as being incorporated into the metal oxide nanoarchitecture/P3HT hybrid. Compared to the metal oxide nanoarchitecture/P3HT hybrid solar cell, a 30% enrichment of the short-circuit current density (Jsc) is attained in the P3HT-based nanoarchitectural Fano solar cell with the Au@silica NPs. The enhancement of charge separation in the cell by the electric field of the Fano resonance is directly evidenced by time-resolved photoluminescence measurements. The increase of the degree of P3HT order in the hybrid by the incorporation of Au@silica NPs into the hybrid active layer may also contribute to the enhancement in the Jsc. Charge carrier dynamic measurements show that an electron collection efficiency of ∼97% can be maintained in the P3HT-based nanoarchitectural Fano solar cell. Significant improvement of the efficiency of the inverted metal oxide/P3HT hybrid solar cell is therefore achieved.

Fabrication of stable photovoltachromic cells using a solvent-free hybrid polymer electrolyte.

In this work, photovoltachromic cells (PVCCs) are fabricated using a solvent-free polyethylene glycol (PEG)-titanium hybrid polymer electrolyte. With appropriate addition of 1,2-dimethyl-3-propylimidazolium iodide in the electrolyte, the range of tunable colored-state transmittance of the PVCC is enlarged due to an improved fill factor. A transmittance modulation larger than 40% can be maintained for at least 3 months, demonstrating the good long-term stability of PVCCs fabricated using the solvent-free PEG-Ti hybrid electrolyte.

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques.

Efforts have been made to elucidate the origin of d(0) magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.

Room-temperature chemical integration of ZnO nanoarchitectures on plastic substrates for flexible dye-sensitized solar cells.

ZnO nanoarchitectured anodes composed of the ZnO nanocactus array and the top ZnO particle layer are chemically integrated on ITO-PET substrates using a facile room-temperature chemical bath deposition method for dye-sensitized solar cells (DSSCs). In the absence of high-temperature post-treatment and mechanical compression, a notable efficiency of 5.24% is simply achieved in the flexible ZnO DSSC.

Synergistic effect of dual interfacial modifications with room-temperature-grown epitaxial ZnO and adsorbed indoline dye for ZnO nanorod array/P3HT hybrid solar cell.

ZnO nanorod (NR)/poly(3-hexylthiophene) (P3HT) hybrid solar cells with interfacial modifications are investigated in this work. The ZnO NR arrays are modified with room-temperature (RT)-grown epitaxial ZnO shells or/and D149 dye molecules prior to the P3HT infiltration. A synergistic effect of the dual modifications on the efficiency of the ZnO NR/P3HT solar cell is observed. The open-circuit voltage and fill factor are considerable improved through the RT-grown ZnO and D149 modifications in sequence on the ZnO NR array, which brings about a 2-fold enhancement of the efficiency of the ZnO NR/P3HT solar cell. We suggested that the more suitable surface of RT-grown ZnO for D149 adsorption, the chemical compatibility of D149 and P3HT, and the elevated conduction band edge of the RT-grown ZnO/D149-modified ZnO NR array construct the superior interfacial morphology and energetics in the RT-grown ZnO/D149-modified ZnO NR/P3HT hybrid solar cell, resulting in the synergistic effect on the cell efficiency. An efficiency of 1.16% is obtained in the RT-grown ZnO/D149-modified ZnO NR/P3HT solar cell.

Morphology and interfacial energetics controls for hierarchical anatase/rutile TiO2 nanostructured array for efficient photoelectrochemical water splitting.

In this work, a three-dimensional (3D) hierarchical TiO2 nanostructured array is constructed on the basis of the considerations of morphology and interfacial energetics for photoelectrochemical water splitting. The photoelectrode is composed of a core-shell structure where the core portion is a rutile TiO2 nanodendrite (ND) array and the shell portion is rutile and anatase TiO2 nanoparticles (NPs) sequentially located on the surface. The TiO2 ND array provides a fast electron transport pathway due to its quasi-single-crystalline structure. The 3D configuration with NPs in the shell portion provides a larger surface area for more efficient photocharge separation without significantly sacrificing the electron collection efficiency. Moreover, anatase TiO2 NPs constructed on the surface of the ND/rutile TiO2 NP nanostructured array enhance charge separation and suppress charge recombination at the interfacial region due to the higher conduction band edge of anatase TiO2 compared to that of rutile TiO2. A photocurrent density and photoconversion efficiency of 2.08 mA cm(-2) at 1.23 V vs reversible hydrogen electrode (RHE) and 1.13% at 0.51 V vs RHE are, respectively, attained using the hierarchical TiO2 nanostructured array photoelectrochemical cell under illumination of AM 1.5G (100 mW cm(-2)).

Fuel-assisted solution route to nanostructured nickel oxide films for electrochromic device application.

In this work, nanocrystalline NiO films were prepared using the fuel-assisted solution method. The microstructure of the NiO film can be modulated by the addition of thiourea fuel. The size of NiO nanocrystals in the NiO film decreased with increasing amount of thiourea in the precursor solution. Compared to the film prepared without thiourea addition, the thiourea-assisted NiO film had enhanced electrochromic properties, including larger transmittance modulation, larger coloration efficiency, faster response time, and superior reliability. Electrochemical impedance spectroscopy measurements indicate that faster charge transfer occurs at the interface between the electrolyte and the fuel-assisted NiO films, which results in improved electrochromic behavior.

Room-temperature fast construction of outperformed ZnO nanoarchitectures on nanowire-array templates for dye-sensitized solar cells.

A ZnO nanoarchitecture composed of nanocactus (NCs) and nanosheets (NSs) is constructed on the ZnO-nanowire (NW)-array template within 4 min by a facile room-temperature (RT) chemical bath deposition (CBD) for use in dye-sensitized solar cells (DSSCs). Compared to the ZnO NW array, the spines and shells of NCs provide larger and more fitting surface for dye adsorption. The NSs developed on the top and side walls of the NWs afford the additional surface for dye adsorption as well as for light scattering. Moreover, the RT-grown ZnO nanostructures possess an upward-shifted conduction band edge and a fast electron transport rate compared to the primary ZnO NW array. With an anode thickness of 9 µm, an efficiency of 5.14% is therefore simply attained in the D149-sensitized ZnO NC-NS DSSC.

Efficient Electron Collection in Hybrid Polymer Solar Cells: In-Situ-Generated ZnO/Poly(3-hexylthiophene) Scaffolded by a TiO2 Nanorod Array.

A nanoarchitectural hybrid polymer solar cell, integrating the ordered and the bulk heterojunction hybrid polymer solar cells, is fabricated by infiltrating the diethylzinc/poly(3-hexylthiophene) (P3HT) solution into the interstices of the TiO2 nanorod (NR) array. An inorganic network composed of tiny ZnO nanocrystals is constructed in the in-situ-generated hybrid within the interstice of the single-crystalline TiO2 NRs. The TiO2 NR array, which possesses a longer electron lifetime and an appropriate electron-transport rate, serves not only as an electron transporter/collector extended from fluorine-doped tin oxide (FTO) electrode to sustain the efficient electron collection but also as a scaffold to hold the sufficient amount of ZnO/P3HT hybrid. The in-situ-generated ZnO/P3HT hybrid layer with superior charge separation efficiency can therefore be thickened in the presence of a TiO2 NR array for increasing the light-harvesting efficiency. A notable efficiency of 2.46% is therefore attained in the TiO2 NR-ZnO/P3HT hybrid solar cell.