Pushing the Limits on Metal-Organic Frameworks as a Catalyst Support: NU-1000 Supported Tungsten Catalysts for o-Xylene Isomerization and Disproportionation.

Acid-catalyzed skeletal C-C bond isomerizations are important benchmark reactions for the petrochemical industries. Among those, o-xylene isomerization/disproportionation is a probe reaction for strong Brønsted acid catalysis, and it is also sensitive to the local acid site density and pore topology. Here, we report on the use of phosphotungstic acid (PTA) encapsulated within NU-1000, a Zr-based metal-organic framework (MOF), as a catalyst for o-xylene isomerization at 523 K. Extended X-ray absorption fine structure (EXAFS), 31P NMR, N2 physisorption, and X-ray diffraction (XRD) show that the catalyst is structurally stable with time-on-stream and that WO x clusters are necessary for detectable rates, consistent with conventional catalysts for the reaction. PTA and framework stability under these aggressive conditions requires maximal loading of PTA within the NU-1000 framework; materials with lower PTA loading lost structural integrity under the reaction conditions. Initial reaction rates over the NU-1000-supported catalyst were comparable to a control WO x-ZrO2, but the NU-1000 composite material was unusually active toward the transmethylation pathway that requires two adjacent active sites in a confined pore, as created when PTA is confined in NU-1000. This work shows the promise of metal-organic framework topologies in giving access to unique reactivity, even for aggressive reactions such as hydrocarbon isomerization.

A dual-functional asymmetric squaraine-based low band gap hole transporting material for efficient perovskite solar cells.

We demonstrate for the first time an asymmetric squaraine-based low band-gap hole transporting material, which acted as both light harvesting and hole transporting layers in methylammonium lead triiodide perovskite solar cells. Opto-electrochemical characterization revealed extremely high molar extinction coefficients of the absorption bands in the low energy region and prominent space charge delocalization due to its electronically asymmetric nature. A suitable band alignment of the squaraine HOMO level with the valence band edge of the perovskite, and the conduction band of the TiO2 with LUMO of the perovskite allowed a cascade of hole extraction and electron injection, respectively. Red-shifted absorption was observed for both HTMs in thin films coated on the perovskite, and the optimized devices exhibited an impressive PCE of 14.7% under full sunlight illumination (100 mW cm(-2), AM1.5 G). The efficiency value is comparable to that of the devices using a state-of-the-art spiro-OMeTAD hole transport layer under similar conditions. Ambient stability after 300 h revealed that 88% of the initial efficiency remained for , and almost no change for , indicating that the devices had good long-term stability thus suggesting that the asymmetric squaraines have great potential as a dual-functional HTM for high performance perovskite solar cells.

Efficient Hole-Transporting Materials with Triazole Core for High-Efficiency Perovskite Solar Cells.

Efficient hole-transporting materials (HTMs), TAZ-[MeOTPA]2 and TAZ-[MeOTPATh]2 incorporating two electron-rich diphenylamino side arms, through direct linkage or thiophen bridges, respectively, on the C3- and C5-positions of a 4-phenyl-1,2,4-triazole core were synthesized. These synthetic HTMs with donor-acceptor type molecular structures exhibited effective intramolecular charge transfer for improving the hole-transporting properties. The structural modification of HTMs by thiophene bridging might increase intermolecular π-π stacking in the solid state and afford a better spectral response because of their increased π-conjugation length. Perovskite-based cells using TAZ-[MeOTPA]2 and TAZ-[MeOTPATh]2 as HTMs afforded high power conversion efficiencies of 10.9 % and 14.4 %, respectively, showing a photovoltaic performance comparable to that obtained using spiro-OMeTAD. These synthetically simple and inexpensive HTMs hold promise for replacing the more expensive spiro-OMeTAD in high-efficiency perovskite solar cells.

Efficient, symmetric oligomer hole transporting materials with different cores for high performance perovskite solar cells.

Novel symmetric oligomer hole transporting materials (HTMs) incorporating 3,4-ethylenedioxythiophene (EDOT) and 2,1,3-benzothiadiazole (BTD) cores have been synthesized and tested for high performance perovskite solar cells. A maximum energy conversion efficiency of 14.23% has been achieved by employing with the electron donating EDOT unit as the core, which is comparable to that of the traditional (14.55%).

Efficient Hole Transporting Materials with Two or Four N,N-Di(4-methoxyphenyl)aminophenyl Arms on an Ethene Unit for Perovskite Solar Cells.

Novel steric bulky hole transporting materials (HTMs) with two or four N,N-di(4-methoxyphenyl)aminophenyl units have been synthesized. When the EtheneTTPA was used as a hole transporting material in perovskite solar cell, the power conversion efficiency afforded 12.77 % under AM 1.5 G illumination, which is comparable to the widely used spiro-OMeTAD based solar cell (13.28 %).

Stable and efficient hole transporting materials with a dimethylfluorenylamino moiety for perovskite solar cells.

Novel star-shaped hole transporting materials (HTMs) with a bis-dimethylfluorenylamino moiety have been synthesized and evaluated for high performance perovskite solar cell applications. Maximum power conversion efficiency of 14.21% has been achieved by using the HTM with a fused TPA core and the long-term stability was also shown to be comparable with that of .

Efficient perovskite solar cells with 13.63 % efficiency based on planar triphenylamine hole conductors.

A new type of hole transporting material (HTMs) with an incorporated planar amine or triphenylamine as a core unit have been prepared. The two amine derivatives were demonstrated to be efficient hole transporting materials in fabricating solid-state organic-inorganic hybrid solar cells. Perovskite-based solar cells with a planar amine derivative gave a short circuit photocurrent density (Jsc) of 20.98 m Acm(-2), an open circuit voltage (Voc) of 0.972 V, and a fill factor of 0.67, corresponding to an overall conversion efficiency of 13.63 %. The photovoltaic performance is comparable to that of the standard spiro-OMeTAD. Moreover, the device showed good stability under light soaking for 500 h. These HTMs hold promise to replace the expensive spiro-OMeTAD because of their high efficiency, excellent stability, synthesis from simple and inexpensive materials.

Star-shaped hole transporting materials with a triazine unit for efficient perovskite solar cells.

Novel star-shaped hole transporting materials with a triazine unit have been synthesized. When the new Triazine-Th-OMeTPA was used as a hole transporting material in perovskite solar cells, the power conversion efficiency reached 12.51% under AM 1.5 G (100 mW cm(-2)) illumination, showing competitive photovoltaic performance with the widely used spiro-OMeTAD based solar cell (13.45%).

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.

Electron-rich anthracene semiconductors containing triarylamine for solution-processed small-molecule organic solar cells.

New electron-rich anthracene derivatives containing triarylamine hole stabilizers, 2,6-bis[5,5'-bis(N,N'-diphenylaniline)-2,2'-bithiophen-5-yl]-9,10-bis-[(triisopropylsilyl)ethynyl]anthracene (TIPSAntBT-TPA) and 2,6-bis(5,5'-bis{4-[bis(9,9-dimethyl-9H-fluoren-2-yl)amino]phenyl}-2,2'-bithiophen-5-yl)-9,10-bis-[(triisopropylsilyl)ethynyl]anthracene (TIPSAntBT-bisDMFA), linked with π-conjugated bithiophene bridges, were synthesized and their photovoltaic characteristics were investigated in solution-processed small-molecule organic solar cells (SMOSCs). These new materials exhibited superior intramolecular charge transfer from triarylamine to anthracene, leading to a more electron-rich anthracene core that facilitated electron transfer into phenyl-C(61)-butyric acid methyl ester. Compared with TIPSAntBT and triarylamine, these materials show a threefold improvement in hole-transporting properties and better photovoltaic performance in solution-processed SMOSCs, with the best power conversion efficiency being 2.96 % at a high open-circuit voltage of 0.85 V.