Highly conductive and stable graphene/PEDOT:PSS composite as a metal free cathode for organic dye-sensitized solar cells.

Platinum (Pt) as the counter electrode (CE) in dye-sensitized solar cells (DSSCs) is expensive and non-optimal for cobalt(ii/iii) redox couples, which can tune and improve the performance of DSSCs, thus motivating the search for replacements of the Pt CE. Graphene nanoplatelets (GnPs) are possible alternatives to Pt CEs but they are mechanically unstable as CEs due to their poor substrate adhesion. Here we report a new type of PEDOT:PSS (PP)/GnP (PPG) composite that maintains the catalytic performance of GnPs with enhanced adhesion to the substrate via a conductive PEDOT matrix. The resultant PPG exhibited extremely low charge-transfer resistance (R ct) compared to Pt in its role as an electrocatalyst toward a Co(bpy)3 2+/3+ (bpy = 2,2'-bipyridine) redox couple, and displayed extremely high electrochemical stability for Co(bpy)3 3+ reduction even after 1000 cycles. The inter-stacking of GnP layers between PEDOT and PSS was confirmed by XPS and Raman spectra. It helps to delocalize charges in the PEDOT backbone and rapidly transfers electrons from the external circuit to Co(bpy)3 3+. This reduces the R ct and ultimately improves the photovoltaic performance. The DSSC based on Y123 sensitizer and PPG-CE showed a higher photovoltaic performance of 8.33% than its Pt counterpart does (7.99%) under the optimized conditions.

Edge-selenated graphene nanoplatelets as durable metal-free catalysts for iodine reduction reaction in dye-sensitized solar cells.

Metal-free carbon-based electrocatalysts for dye-sensitized solar cells (DSSCs) are sufficiently active in Co(II)/Co(III) electrolytes but are not satisfactory in the most commonly used iodide/triiodide (I(-)/I3 (-)) electrolytes. Thus, developing active and stable metal-free electrocatalysts in both electrolytes is one of the most important issues in DSSC research. We report the synthesis of edge-selenated graphene nanoplatelets (SeGnPs) prepared by a simple mechanochemical reaction between graphite and selenium (Se) powders, and their application to the counter electrode (CE) for DSSCs in both I(-)/I3 (-) and Co(II)/Co(III) electrolytes. The edge-selective doping and the preservation of the pristine graphene basal plane in the SeGnPs were confirmed by various analytical techniques, including atomic-resolution transmission electron microscopy. Tested as the DSSC CE in both Co(bpy)3 (2+/3+) (bpy = 2,2'-bipyridine) and I(-)/I3 (-) electrolytes, the SeGnP-CEs exhibited outstanding electrocatalytic performance with ultimately high stability. The SeGnP-CE-based DSSCs displayed a higher photovoltaic performance than did the Pt-CE-based DSSCs in both SM315 sensitizer with Co(bpy)3 (2+/3+) and N719 sensitizer with I(-)/I3 (-) electrolytes. Furthermore, the I3 (-) reduction mechanism, which has not been fully understood in carbon-based CE materials to date, was clarified by an electrochemical kinetics study combined with density functional theory and nonequilibrium Green's function calculations.

Graphene nanoplatelets doped with N at its edges as metal-free cathodes for organic dye-sensitized solar cells.

Challenging precious Pt-based electrocatalysts for dye-sensitized solar cells (DSSCs), graphene nanoplatelets that are N-doped at the edges (NGnPs) are prepared via simply ball-milling graphite in the presence of nitrogen gas. DSSCs based on specific nanoplatelets designated "NGnP5" display superior photovoltaic performance (power conversion efficiency, 10.27%) compared to that of conventional Pt-based devices (9.96%). More importantly, the NGnP counter electrode exhibits outstanding electrochemical stability and electrocatalytic activity with a cobalt-complex redox couple.

Tailor-made hole-conducting coadsorbents for highly efficient organic dye-sensitized solar cells.

The Y-shaped, low molecular mass, hole-conductor (HC), acidic coadsorbents 4-{3,7-bis[4-(2-ethylhexyloxy)phenyl]-10H-phenothiazin-10-yl}benzoic acid (PTZ1) and 4-{3,7-bis[4-(2-ethylhexyloxy)phenyl]-10H-phenothiazin-10-yl}biphenyl-4-carboxylic acid (PTZ2) were developed. Owing to their tuned and negative-shifted HOMO levels (vs. NHE), they were used as HC coadsorbents in dye-sensitized solar cells (DSSCs) to improve cell performance through desired cascade-type hole-transfer processes. Their detailed functions as HC coadsorbents in DSSCs were investigated to obtain evidence for the desired cascade-type hole-transfer processes. They have multiple functions, such as preventing π-π stacking of dye molecules, harvesting light of shorter wavelengths, and faster dye regeneration. By using PTZ2 as the tailor-made HC coadsorbent on the TiO2 surface with the organic dye NKX2677, an extremely high conversion efficiency of 8.95 % was achieved under 100 mW cm(-2) AM 1.5G simulated light (short-circuit current JSC =16.56 mA cm(-2) , open-circuit voltage VOC =740 mV, and fill factor of 73 %). Moreover, JSC was increased by 13 %, VOC by 27 % and power-conversion efficiency by 49 % in comparison to an NKX2677-based DSSC without an HC coadsorbent. This is due to the HC coadsorbent having a HOMO energy level well matched to that of the NKX-2677 dye to induce the desired cascade-type hole-transfer processes, which are associated with a slower charge recombination, fast dye regeneration, effective screening of liquid electrolytes, and an induced negative shift of the quasi-Fermi level of the electrode. Thus, this new class of Y-shaped, low molecular weight, organic, HC coadsorbents based on phenothiazine carboxylic acid derivatives hold promise for highly efficient organic DSSCs.

Dye-sensitized solar cells based on organic dual-channel anchorable dyes with well-defined core bridge structures.

In stereo, where available: A new approach towards dye-sensitized solar cells is based on dianchoring structural motifs with two donors, two acceptors, and a core bridge donor as a spacer. Their high molar absorption coefficients result in favorable light-harvesting efficiencies for DSSCs based on these dyes. A high conversion efficiency of 4.90 % is achieved when using dye DC4, containing a core bridge carbazole unit, with a multifunctional coadsorbent.

Direct nitrogen fixation at the edges of graphene nanoplatelets as efficient electrocatalysts for energy conversion.

Nitrogen fixation is essential for the synthesis of many important chemicals (e.g., fertilizers, explosives) and basic building blocks for all forms of life (e.g., nucleotides for DNA and RNA, amino acids for proteins). However, direct nitrogen fixation is challenging as nitrogen (N2) does not easily react with other chemicals. By dry ball-milling graphite with N2, we have discovered a simple, but versatile, scalable and eco-friendly, approach to direct fixation of N2 at the edges of graphene nanoplatelets (GnPs). The mechanochemical cracking of graphitic C--C bonds generated active carbon species that react directly with N2 to form five- and six-membered aromatic rings at the broken edges, leading to solution-processable edge-nitrogenated graphene nanoplatelets (NGnPs) with superb catalytic performance in both dye-sensitized solar cells and fuel cells to replace conventional Pt-based catalysts for energy conversion.

Organic sensitizers featuring a planar indeno[1,2-b]-thiophene for efficient dye-sensitized solar cells.

An efficient organic sensitizer (JK-306) featuring a planar indeno[1,2-b]thiophene as the π-linker of a bridging unit for dye-sensitized solar cells (DSSCs) was synthesized. The sensitizer had a strong molar absorption coefficient and a red-shifted absorption band compared with JK-305, which resulted in a significant increase in the short-circuit photocurrent density. We incorporated a highly congested bulky amino group into the 2',4'-dihexyloxybiphenyl-4-yl moiety, an electron donor, to diminish the charge recombination and to prevent aggregation of the sensitizer. Under standard AM 1.5G solar conditions, JK-306-sensitized cells in the presence of co-adsorbents chenodeoxycholic acid (CDCA) and 4-[bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzoic acid (HC-A), which afforded an overall conversion efficiency of 8.37% and 8.52%, respectively. Upon changing the I(-) /I3 (-) electrolyte to the Co(II) /Co(III) redox couple, the cell gave rise to a significantly improved conversion efficiency of 10.02% with the multifunctional HC-A, which is one of the highest values reported for DSSCs with a cobalt-based electrolyte. Furthermore, the JK-306-based solar cell with a polymer gel electrolyte revealed a high conversion efficiency of 7.61%, which is one of the highest values for cells based on organic sensitizers.

N-Doped graphene nanoplatelets as superior metal-free counter electrodes for organic dye-sensitized solar cells.

Highly efficient counter electrodes (CEs) for dye-sensitized solar cells (DSSCs) were developed using thin films of scalable and high-quality, nitrogen-doped graphene nanoplatelets (NGnP), which was synthesized by a simple two-step reaction sequence. The resultant NGnP was deposited on fluorine-doped SnO2 (FTO)/glass substrates by using electrospray (e-spray) coating, and their electrocatalytic activities were systematically evaluated for Co(bpy)3(3+/2+) redox couple in DSSCs with an organic sensitizer. The e-sprayed NGnP thin films exhibited outstanding performances as CEs for DSSCs. The optimized NGnP electrode showed better electrochemical stability under prolonged cycling potential, and its Rct at the interface of the CE/electrolyte decreased down to 1.73 Ω cm(2), a value much lower than that of the Pt electrode (3.15 Ω cm(2)). The DSSC with the optimized NGnP-CE had a higher fill factor (FF, 74.2%) and a cell efficiency (9.05%), whereas those of the DSSC using Pt-CE were only 70.6% and 8.43%, respectively. To the best of our knowledge, the extraordinarily better current-voltage characteristics of the DSSC-NGnP outperforming the DSSC-Pt for the Co(bpy)3(3+/2+) redox couple (in paticular, FF and short circuit current, Jsc) is highlighted for the first time.

Novel D-π-A structured Zn(II)-porphyrin dyes containing a bis(3,3-dimethylfluorenyl)amine moiety for dye-sensitised solar cells.

A high solar-to-electricity conversion efficiency of 7.22% was achieved with a short circuit current (J(sc)) of 15.30 mA cm(-2), an open circuit voltage (V(oc)) of 669 mV and a fill factor (FF) of 0.71 for the 2Flu-ZnP-CN-COOH dye with a multi-functional co-adsorbent, under 100 mW cm(-2) AM 1.5 G simulated light.

A new class of cyclometalated ruthenium sensitizers of the type CNN for efficient dye-sensitized solar cells.

A new class of cyclometalated ruthenium sensitizers incorporating a CNN ligand and conjugated 2,2'-bipyridine in the ancillary ligand have been designed and synthesized. The photovoltaic performance of JK-206 using an electrolyte containing 0.6 M 1,2-dimethyl-3-propylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butylpyridine in CH(3)CN gave a short-circuit photocurrent density of 19.63 mA cm(-2), an open-circuit voltage of 0.74 V, and a fill factor of 0.72, affording an overall conversion efficiency of 10.39%. The efficiency is the highest one reported for dye-sensitized solar cells based on the cyclometalated ruthenium sensitizer of the type CNN. Moreover, the same device using a polymer gel electrolyte exhibited a remarkable stability under 1000 h of light soaking at 60 °C, retaining 91% of the initial efficiency of 7.14%.

Landmine detection: improved binding of 2,4-dinitrotoluene in a gamma-CD/metal oxide matrix and its sensitive detection via a cyclic surface polarization impedance (cSPI) method.

Highly sensitive and selective detection of 2,4-DNT, a representative explosive, was achieved by the synergic effect of molecular imprinting and host (cyclodextrin)-guest interaction in ultrathin layers of TiO(2) and SiO(2) gel; the detection limit using cSPI measurements reached nM concentration.

Design of highly efficient receptor sites by combination of cyclodextrin units and molecular cavity in TiO2 ultrathin layer.

A highly effective approach was developed for sensitive detection of organic substances in water. In order to achieve high sensitivity and selective detection for aromatic compounds, cyclodextrin (CD) hosts and imprinting effects were combined to fabricate binding sites within TiO(2) ultrathin layer. The electrode surface was modified with ultrathin TiO(2) gel film containing a 2:1 complex of beta-CD and bisphenol A (BPA), and then the BPA moiety was removed by washing. The resulting BPA-imprinted TiO(2)/beta-CD film showed specific and sensitive detection of BPA, as confirmed by quartz crystal microbalance (QCM) and cyclic surface-polarization impedance (cSPI) measurements. The high selectivity for BPA relative to structurally related guest molecules was estimated to be 1.6-3.4 at the guest concentration of 2x10(-7)M, and was considered to arise from the synergic effect of the binding site.