A combination of fluorine-induced effect and co-sensitization for highly efficient and stable dye-sensitized solar cells.

Developing dyes with high open-circuit photovoltage (Voc) is a vital strategy to improve the power conversion efficiency (PCE) of co-sensitized solar cells (co-DSSCs). Herein, three organic fluorine-containing dyes [YY-ThP(3F), YY-ThP(2F), and YY-ThP(26F)] are designed and synthesized for investigating the fluorine-induced effect on photophysical and photovoltaic performances. Consequently, this effect can significantly broaden the UV-vis absorption spectra of dyes but fail to improve the light-harvesting capability of DSSCs. Strikingly, YY-ThP(3F), featuring 3-position fluorine substitution to cyanoacrylic acid, yields a relatively high Voc compared to the corresponding fluorine-free dye (YY-ThP). Furthermore, the co-sensitization of YY-ThP+YY-ThP(3F) achieves a remarkably high PCE and long-term stability. This work implies that the combination of judicious molecular engineering and co-sensitization is a promising strategy for highly efficient and stable DSSCs.

Fluorination Improves the Electro-Optical Properties of Benzoxazole-Terminated Liquid Crystals in High Birefringence Liquid Crystal Mixtures: Experimental and Theoretical Investigations.

Aromatic heterocyclic liquid crystal (LC) materials have received much attention from LC chemists for their high birefringence and large dielectric anisotropy, yet few have reported their properties in LC mixtures. In this work, a series of fluorinated benzoxazole liquid crystal compounds were synthesized to evaluate their electro-optical properties in high birefringence LC mixtures, with the expectation of further establishing the theoretical basis and experimental evidence for their applications in LC photonics. Firstly, the effects of the lateral fluorine substituent positions on the molecular synthetic yield, mesomorphic and solubility properties were comparatively investigated. Afterwards, we focused on the fluorination effects on the core electro-optical properties, including birefringence, dielectric anisotropy and further investigation of the viscoelastic coefficient of high birefringence LC mixtures. Research results showed that the benzoxazole liquid crystal compounds possess low melting points, wide nematic phase intervals and good solubility by appropriate lateral fluorine substitution, which is beneficial to further improve the electro-optical properties of high birefringence LC mixtures. Meanwhile, the theoretical and experimental results corroborate each other to well reveal the structure-property relationship. This study demonstrates that fluorination would promote promising applications of benzoxazole-terminated liquid crystals in emerging LC optical devices.

Tuning active sites for highly efficient bifunctional oxygen electrocatalysts of rechargeable zinc-air battery.

High activity, excellent durability, and low-cost oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts are highly required for rechargeable zinc (Zn)-air batteries. Herein, we designed an electrocatalyst by integrating the ORR active species of ferroferric oxide (Fe3O4) and the OER active species of cobaltous oxide (CoO) into the carbon nanoflower. By well regulating and controlling the synthesis parameters, Fe3O4 and CoO nanoparticles were uniformly inserted into the porous carbon nanoflower. This electrocatalyst can reduce the potential gap between the ORR and OER to 0.79 V. The Zn-air battery assembled with it exhibited an open-circuit voltage of 1.457 V, a stable discharge of 98 h, a high specific capacity of 740 mA h g-1, a large power density of 137 mW cm-2, as well as good charge/discharge cycling performance, exceeding the performance of platinum/carbon (Pt/C). This work provides references for exploring highly efficient non-noble metal oxygen electrocatalysts by tuning ORR/OER active sites.

Difluorovinyl Liquid Crystal Diluters Improve the Electro-Optical Properties of High-∆n Liquid Crystal Mixture for AR Displays.

A liquid crystal (LC) mixture in liquid crystal on silicon (LCoS) is the core material for augmented reality (AR) displays. However, a LC mixture with high birefringence (Δn) and large dielectric anisotropy (Δε) possesses high viscosity (γ1), which results in a slow response time of LCoS devices for AR displays. This work proposes to apply difluorovinyl-based LC diluters to fine balance the low viscosity, high ∆n, and large ∆ε of the LC mixture for a fast response time. Through studying their effects on the key electro-optical properties of a high-∆n LC mixture, it is found that doping these diluter molecules to a high-∆n LC mixture can decrease the viscoelastic coefficient (γ1/K11), increase ∆ε and the figure of merit, maintain a wide nematic phase temperature range, a high clearing point, and ∆n. It also means that these diluters could effectively regulate the relationship between ∆n, ∆ε, and γ1 in the LC mixtures to achieve a fine balance of various excellent properties and further improve the LC device's response time. The widespread applications of these liquid crystal diluters in emerging liquid crystal optical devices are foreseeable.

Spontaneous Interface Healing by a Dynamic Liquid-Crystal Transition for High-Performance Perovskite Solar Cells.

Low-temperature solution processing of thin-film semiconductors is more cost-effective than traditional vacuum processing; however, it leads to more defects during fast bulk crystallization and residual tensile stress. Herein, a new strategy of dynamic liquid-crystal transition (DLCT) is developed to solve these problems in one step. The design principle is used to suggest that the DLCT molecule should firstly interact with the perovskite grains in the bulk and meanwhile go through a dynamic transition to spontaneously heal the interface. A thermotropic LC molecule (CBO6SS6OCB) is then designed to demonstrate the strategy. The LC interacting with perovskite colloid forms an intermediate adduct to retard the crystallization. The annealing processes stimulate the concentrated LC solid, causing it to flow to the electron transport layer to release the residual stress to attain improved electron extraction. Consequently, the device efficiency is increased to 24.38%, where its VOC of 1.184 V is among the best for the formamidine-based perovskite solar cells. Furthermore, the ambient stability (93.0% of initial efficiency after 2000 h of aging) and light stability (96.3% of initial efficiency after 500 h of aging) are much improved. This work conceives a new engineering of additive phase transition for high-performance perovskite solar cells.

An optimal molecule-matching co-sensitization system for the improvement of photovoltaic performances of DSSCs.

Three biphenyl co-sensitizers (4OBA, 8OBA and 12OBA) with different terminal oxyalkyl chains were synthesized and co-sensitized respectively with the main dye (NP-1) in co-sensitized solar cells (co-DSSCs). The effects of the terminal oxyalkyl chains on the photophysical, electrochemical and photovoltaic properties of the co-DSSCs were systematically investigated. The optimal molecular matching relationship between the co-sensitizers and the main dye was obtained through density functional theory (DFT) calculations. Consequently, 4OBA has the most appropriate three-dimensional (3D) molecular structure, which could not only fill the gap between the large-size dyes but also plays a partial shielding role, inhibiting dye aggregation and electron recombination, therefore yielding the highest power conversion efficiency (PCE) for the co-DSSCs with NP-1@4OBA. This study suggests that adjusting the terminal oxyalkyl chains of the co-sensitizers can be used to enhance the intramolecular charge transfer efficiency and inhibit electron recombination, ultimately improving the photovoltaic performances of the co-DSSCs.

Effect of Extending the Conjugation of Dye Molecules on the Efficiency and Stability of Dye-Sensitized Solar Cells.

We designed and synthesized two organic dyes (A6 and A10) for dye-sensitized solar cells (DSSCs) by extending the molecular conjugation strategy. The sensitizer A10 was constructed by inserting ethene into our previously reported sensitizer AZ6. The sensitizer A6 was obtained by further substituting the hydrogen of ethene with another donor (D) and π-bridge-acceptor (π-A) segment. The UV-vis spectra and J-V curves showed that the dyes A10 and A6 could effectively facilitate the light-harvesting and photocurrent densities with respect to AZ6. Consequently, the A10-based DSSC achieved an enhanced efficiency (8.54%) with a high photocurrent (18.81 mA cm-2). Desorption experiments of dyes adsorbed on TiO2 showed that compared with the monoanchoring dyes AZ6 and A10, the dianchoring configuration effectively strengthened the affinity of dye A6 with the photoanode, making it more difficult to leach from the photoanode. The A6-based DSSC shows outstanding stability, and its overall efficiency could remain 98.0% of its initial value after 3000 h of aging time, exceeding that of its monoanalogue AZ6 (remained 78.3% after 3000 h).

Effect of the Spatial Configuration of Donors on the Photovoltaic Performance of Double D-π-A Organic Dyes.

Three double D-π-A sensitizers (A1, A3, and A5) containing different donors (triphenylamine, methoxy-modified triphenylamine, and cyclic thiourea-functionalized triphenylamine) are synthesized to investigate the role of different donors in dye-sensitized solar cells (DSSCs). Detailed investigations of the sensitizers reveal that the spatial characteristics of donor units have a considerable impact on the light-harvesting, electrochemistry, and photovoltaic properties. Benefiting from the strong shielding ability of alkyl chains in the donor to its branch chains as observed in density functional theory (DFT), the open-circuit voltage (VOC = 712.0 mV) of A5-based DSSC is higher than those of A1 and A3 by 90 and 78 mV, respectively. Therefore, the A5-based DSSC delivers a good efficiency of 8.54%, relying on its effective suppression of interfacial recombination. The results indicate that the judiciously tailored donor unit is an effective approach to optimize dye configurations to further improve power conversion efficiencies.

Highly Active Hollow RhCu Nanoboxes toward Ethylene Glycol Electrooxidation.

The efficient electrocatalysts toward the ethylene glycol oxidation reaction (EGOR) are highly desirable for direct ethylene glycol fuel cells because of the sluggish kinetics of anodic EGOR. Herein, porous RhCu nanoboxes are successfully prepared through facile galvanic replacement reaction and succedent sodium borohydride reduction strategy. Benefiting from hierarchical pore structure, RhCu nanoboxes display excellent electrocatalytic performance toward the EGOR in alkaline medium with a mass activity of 775.1 A gRh -1 , which is 2.8 times as large as that of commercial Rh nanocrystals. Moreover, the long-term stability of RhCu nanoboxes is better than that of commercial Rh nanocrystals. Furthermore, the theoretical calculations demonstrate that RhCu nanoboxes possess lower adsorption energy of CO and lower reaction barrier (0.27 eV) for the COads oxidation with aid of the adsorbed OHads species, resulting in the outstanding electrocatalytic performance toward the EGOR. This work provides a meaningful reference for developing highly effective electrocatalysts toward the EGOR.

Synthesis and characterization of a novel crosslinkable side-chain sulfonated poly(arylene ether sulfone) copolymer proton exchange membranes.

A series of novel crosslinkable side-chain sulfonated poly(arylene ether sulfone) copolymers (S-SPAES(x/y)) was prepared from 4,4'-biphenol, 4,4'-difluorodiphenyl sulfone, and a new difluoro aromatic monomer 1-(2,6-difluorophenyl)-2-(3,5-dimethoxyphenyl)-1,2-ethanedione (DFDMED) via co-polycondensation, demethylation, and further nucleophilic substitution of 1,4-butane sultone. Meanwhile, quinoxaline-based crosslinked copolymers (CS-SPAES(x/y)) were obtained via cyclo-condensation between S-SPAES(x/y) and 3,3'-diaminobenzidine. Both the crosslinkable and crosslinked copolymer membranes exhibit good mechanical properties and high anisotropic membrane swelling. Crosslinkable S-SPAES(1/2) with an ion exchange capacity (IEC) of 2.01 mequiv. g-1 displays a relatively high proton conductivity of 180 mS cm-1 and acceptable single-cell performance, which is attributed to its good microphase separation resulting from the side-chain sulfonated copolymer structures. Compared with S-SPAES(1/1) (IEC of 1.68 mequiv. g-1), crosslinked CS-SPAES(1/2) with a comparable IEC exhibits a larger conductivity of 157 mS cm-1, and significantly higher oxidative stability and lower membrane swelling, suggesting a distinct performance improvement due to the quinoxaline-based crosslinking.

In situ conversion of iron sulfide (FeS) to iron oxyhydroxide (γ-FeOOH) on N, S co-doped porous carbon nanosheets: An efficient electrocatalyst for the oxygen reduction reaction and zinc-air batteries.

For the development of metal-air batteries and fuel cells, highly efficient and inexpensive electrocatalysts are one of the main issues for scalable applications of these advanced energy devices. Herein, based on the in situ conversion of FeS to γ-FeOOH with a two-dimensional (2D) layered structure, a special nanohybrid, N, S co-doped porous carbon nanosheets loaded with γ-FeOOH, is fabricated by carbonization of Fe3+-coordinated polydopamine, which uniformly coats the surface of bacterial cellulose. The nanocomposites exhibit high activity towards the cathodic oxygen reduction reaction (ORR), characterized by a more positive half-wave potential (10 mV) than the commercial Pt/C (20 wt%) electrocatalyst in alkaline medium. Additionally, the nanohybrid has excellent stability and a high methanol tolerance towards the ORR. Further experiments and density functional theory (DFT) calculations demonstrate that the doped N, S in the carbon matrix and the (0 1 0) plane of γ-FeOOH are the ORR active sites. A zinc-air battery equipped with this nanohybrid presents better a power density (92 mW cm-2) and specific capacity (740 mA h g-1) than the Pt/C electrocatalyst, demonstrating its promising potential for application in energy conversion devices.

0.2 V Electrolysis Voltage-Driven Alkaline Hydrogen Production with Nitrogen-Doped Carbon Nanobowl-Supported Ultrafine Rh Nanoparticles of 1.4 nm.

The development of highly effective and low-cost electrocatalysts for energy-saving hydrogen production via water splitting is still a great challenge. Herein, porous nitrogen-doped carbon nanobowls (N-CBs) have been designed and used for the controlled growth of ultrafine rhodium (Rh) nanoparticles. With the aid of interfacial bonding of Rh and N, ultrafine Rh nanoparticles with an average size of 1.4 nm have been successfully immobilized on the N-CBs. This Rh/N-CB electrocatalyst shows superior activity and high stability for the hydrogen evolution reaction (HER) and the hydrazine oxidation reaction (HzOR). More importantly, the Rh/N-CBs exhibit high activity for hydrogen production from water electrolysis, marking with a cell voltage of 0.2 V to achieve a current density of 20 mA cm-2 when they serve as cathodic electrocatalysts for the HER and anodic electrocatalysts for the HzOR in 1 M KOH with 0.5 M hydrazine. The density functional theory calculations demonstrate that a near-zero hydrogen adsorption free energy produced by the chemical bonding of Rh with the pyrrole-N doped in N-CBs is responsible for the excellent HER activity of Rh/N-CBs electrocatalysts.

Rice OsDOF15 contributes to ethylene-inhibited primary root elongation under salt stress.

In early seedlings, the primary root adapts rapidly to environmental changes through the modulation of endogenous hormone levels. The phytohormone ethylene inhibits primary root elongation, but the underlying molecular mechanism of how ethylene-reduced root growth is modulated in environmental changes remains poorly understood. Here, we show that a novel rice (Oryza sativa) DOF transcription factor OsDOF15 positively regulates primary root elongation by regulating cell proliferation in the root meristem, via restricting ethylene biosynthesis. Loss-of-function of OsDOF15 impaired primary root elongation and cell proliferation in the root meristem, whereas OsDOF15 overexpression enhanced these processes, indicating that OsDOF15 is a key regulator of primary root elongation. This regulation involves the direct interaction of OsDOF15 with the promoter of OsACS1, resulting in the repression of ethylene biosynthesis. The control of ethylene biosynthesis by OsDOF15 in turn regulates cell proliferation in the root meristem. OsDOF15 transcription is repressed by salt stress, and OsDOF15-mediated ethylene biosynthesis plays a role in inhibition of primary root elongation by salt stress. Thus, our data reveal how the ethylene-inhibited primary root elongation is finely controlled by OsDOF15 in response to environmental signal, a novel mechanism of plants responding to salt stress and transmitting the information to ethylene biosynthesis to restrict root elongation.

Graphene-Encapsulated Co9 S8 Nanoparticles on N,S-Codoped Carbon Nanotubes: An Efficient Bifunctional Oxygen Electrocatalyst.

An inexpensive and efficient bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is central to the rechargeable zinc-air battery. Herein, a nanohybrid, in which N,S-codoped carbon nanotubes were decorated with Co9 S8 nanoparticles encapsulated in porous graphene layers, was fabricated by a one-step heat-treatment process. The N,S dopant species were the major active sites for the ORR, and Co9 S8 nanoparticles were mainly responsible for the OER. Compared with commercial 20 wt % Pt/C and Ir/C electrocatalysts, this nanohybrid exhibited a comparable ORR half-wave potential (0.831 V vs. reversible hydrogen electrode) and OER potential (1.591 V at 10 mA cm-2 ), better long-term stability in an alkaline medium, and a narrower potential gap (0.76 V) between ORR and OER. Furthermore, as air electrode of the rechargeable zinc-air battery, it delivered a low charge-discharge voltage gap (0.65 V at 5 mA cm-2 ), high open-circuit potential (1.539 V), good specific capacity (805 mA h g - 1 Zn at 5 mA cm-2 ), and excellent cycling stability (48 h), superior to those of commercial Pt/C and Ir/C catalysts, and thus showed promise for applications in renewable energy conversion devices.

Interface self-assembly preparation of multi-element doped carbon nanobowls with high electrocatalysis activity for oxygen reduction reaction.

Developing an efficient, stable and low cost oxygen reduction reaction electrocatalyst is desirable for fuel cells and metal-air batteries. Here, we have successfully prepared multi-element doped carbon nanobowls by simply mixing the porous carbon nanobowls and sulfur doped graphitic carbon nitride quantum dots in FeCl3 solution and subsequent high temperature treatment processes. Compared with the commercial Pt/C electrocatalyst, the multi-element doped carbon nanobowls display a comparable half-wave potential of 0.82 V, much larger limiting diffusion current density (0.4-0.8 V), better methanol-tolerance and higher long-term stability for the oxygen reduction reaction in alkaline media. The robust three-dimensional porous structure of carbon nanobowls and multiple active centers derived from Fe, N, S and O co-doping are responsible for the excellent performance. This work suggests that such multi-element doped carbon nanobowls can be a promising alternative for Pt-based catalysts in fuel cells.

The activation of OsEIL1 on YUC8 transcription and auxin biosynthesis is required for ethylene-inhibited root elongation in rice early seedling development.

Rice is an important monocotyledonous crop worldwide; it differs from the dicotyledonous plant Arabidopsis in many aspects. In Arabidopsis, ethylene and auxin act synergistically to regulate root growth and development. However, their interaction in rice is still unclear. Here, we report that the transcriptional activation of OsEIL1 on the expression of YUC8/REIN7 and indole-3-pyruvic acid (IPA)-dependent auxin biosynthesis is required for ethylene-inhibited root elongation. Using an inhibitor of YUC activity, which regulates auxin biosynthesis via the conversion of IPA to indole-3-acetic acid (IAA), we showed that ethylene-inhibited primary root elongation is dependent on YUC-based auxin biosynthesis. By screening phenotypes of seedling primary root from mutagenesis libraries following ethylene treatment, we identified a rice ethylene-insensitive mutant, rein7-1, in which YUC8/REIN7 is truncated at its C-terminus. Mutation in YUC8/REIN7 reduced auxin biosynthesis in rice, while YUC8/REIN7 overexpression enhanced ethylene sensitivity in the roots. Moreover, YUC8/REIN7 catalyzed the conversion of IPA to IAA, truncated version at C-terminal end of the YUC8/REIN7 resulted in significant reduction of enzymatic activity, indicating that YUC8/REIN7 is required for IPA-dependent auxin biosynthesis and ethylene-inhibited root elongation in rice early seedlings. Further investigations indicated that ethylene induced YUC8/REIN7 expression and promoted auxin accumulation in roots. Addition of low concentrations of IAA rescued the ethylene response in the rein7-1, strongly demonstrating that ethylene-inhibited root elongation depends on IPA-dependent auxin biosynthesis. Genetic studies revealed that YUC8/REIN7-mediated auxin biosynthesis functioned downstream of OsEIL1, which directly activated the expression of YUC8/REIN7. Thus, our findings reveal a model of interaction between ethylene and auxin in rice seedling primary root elongation, enhancing our understanding of ethylene signaling in rice.

High electrocapacitive performance of bowl-like monodispersed porous carbon nanoparticles prepared with an interfacial self-assembly process.

Bowl-like monodispersed porous carbon nanoparticles (BMPCNs) have been successfully prepared with a facile and scalable approach, and the as-prepared BMPCNs are examined thoroughly by various physical characterizations. Physical measurements display that BMPCNs have the high surface area (1255m2g-1), hierarchical porosity, a certain amount of oxygen-containing groups and high graphitization degree. These unique structure features endow BMPCNs with a high capacitance (281Fg-1 at 0.5Ag-1), excellent rate capability (209Fg-1 at 50Ag-1), and outstanding cycling stability (94.8% capacity retention after 10,000 cycles at 10Ag-1) in electrochemical double-layer capacitors, suggesting its promising applications in field of energy conversion and storage. Further, the studies on formation mechanism of BMPCNs suggest that, the CTAB wormlike micelles assembling with silica/resorcinol-formaldehyde oligomers at the interface of tetraethyl orthosilicate droplets under Stöber condition determines the morphology of BMPCNs.

Syngas production by high temperature steam/CO2 coelectrolysis using solid oxide electrolysis cells.

High temperature (HT) steam/CO2 coelectrolysis with solid oxide electrolysis cells (SOECs) using the electricity and heat generated from clean energies is an important alternative for syngas production without fossil fuel consumption and greenhouse gas emissions. Herein, reaction characteristics and the outlet syngas composition of HT steam/CO2 coelectrolysis under different operating conditions, including distinct inlet gas compositions and electrolysis current densities, are systematically studied at 800 °C using commercially available SOECs. The HT coelectrolysis process, which has comparable performance to HT steam electrolysis, is more active than the HT CO2 electrolysis process, indicating the important contribution of the reverse water-gas shift reaction in the formation of CO. The outlet syngas composition from HT steam/CO2 coelectrolysis is very sensitive to the operating conditions, indicating the feasibility of controlling the syngas composition by varying these conditions. Maximum steam and CO2 utilizations of 77% and 76% are achieved at 1.0 A cm(-2) with an inlet gas composition of 20% H2/40% steam/40% CO2.

An all solid-state high-voltage ns trigger generator based on magnetic pulse compression and transmission line transformer.

Innovative design of an all solid-state high-voltage ns trigger generator, based on magnetic pulse compression and transmission line transformer, is presented. The repetitive trigger pulse generator was developed to trigger a 700 kV trigatron, which has been used to pulse a repetitive intense electron beam accelerator with Tesla transformer charged double pulse forming lines (PFLs). Experimental results show that the trigger pulse generator could produce 180 kV 65 ns duration pulses with a rise time of 20 ns. The repetitive trigger pulses have nice uniform in the voltage waveform. The control time jitter is less then 3 ns. Owing to its good stability and low time jitter, the high-voltage trigger generator is an excellent candidate to trigger the repetitive accelerator.

Cyclic thiourea/urea functionalized triphenylamine-based dyes for high-performance dye-sensitized solar cells.

Six cyclic thiourea/urea functionalized triphenylamine-based dyes (AZ1-AZ6) containing 2-cyanoacrylic acid as an acceptor and various linkers (phenyl, biphenyl, and bithiophene) were synthesized. They exhibited high photovoltaic performance owing to an improved short-circuit photocurrent density (J(sc)) and open-circuit voltage (V(oc)). Among them, AZ6 bearing a cyclic thiourea group and bithiophene linker showed the highest power conversion efficiency (PCE) up to 7.29%, which was comparable to that of N719 (PCE = 7.36%).