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This study reports the solar light-driven activation of a bicyclic aminoxyl mediator to achieve C–C bond cleavage of a lignin model compound at room temperature using a donor–π-conjugated bridge–acceptor organic dye-based photoelectrochemical system.

A Spiro fluorene-based dopant-free hole-transporting material denoted as Spiro-IA has been designed and developed from inexpensive starting materials with high yield via a simple synthetic approach for application in perovskite solar cells (PSCs). The unit cost of Spiro-IA can be as low as 1/9th that of the conventional Spiro-OMeTAD. Moreover, Spiro-IA shows good solubility in different organic solvents, e.g. CHCl3, acetone, EtOH, and DMF, and showed favorable charge-transport ability and greater photocurrent density compared to Spiro-OMeTAD. The UV absorption/emission spectra of Spiro-IA (λmax = 430 nm, Emax = 601 nm) are red shifted compared to those of Spiro-OMeTAD (λmax = 388 nm, Emax = 414 nm) with larger stokes shift values (171 nm) which helps suppress the loss of incident photons absorbed by the HTM and is more beneficial for improving the performance of PSCs. Optical and electrochemical studies show that Spiro-IA fulfilled the basic requirements of the hole transfer and electron regeneration process in the fabricated devices. PSCs fabricated (surface area = 1.02 cm2) with dopant-free Spiro-IA achieved a maximum power conversion efficiency (PCE) of 15.66% (JSC = 22.14 mA cm−2, VOC = 1.042 V, FF = 0.679%), which was comparable to that of the most commonly used Li-doped Spiro-OMeTAD (PCE = 15.93%, JSC = 20.37 mA cm−2, VOC = 1.057 V, FF = 0.74%) and surpassed that of the dopant-free Spiro-OMeTAD (PCE = 9.34%). Additionally, the PSCs based on dopant-free Spiro-IA achieved outstanding long-term stability and favorable conductivity (σ = 2.104 × 10−4 S cm−1) compared to those based on Spiro-OMeTAD (σ = 9.00 × 10−8 S cm−1). DFT studies were performed using Gaussian 09 at the B3LYP/6-31G (d/p) level to investigate their electron cloud delocalization in HOMO/LUMO levels. These results showed that Spiro-IA could be a promising candidate for low-cost PSC technology and has a great chance to supersede the expensive Spiro-OMeTAD.

Conventional, high-efficiency, hybrid organic–inorganic perovskites (e.g., methylammonium lead iodide (MAPbI3) and formamidinium lead iodide (FAPbI3)) having ammonium-based organic cations exhibit poor moisture stability mainly due to the effective hydrogen bonding interaction of nitrogen in the ammonium-based cations with water molecules. Recently, a sulfonium-based cation, trimethylsulfonium (TMS+), has attracted growing attention for the development of moisture-stable hybrid perovskite solar cells (PSCs). This research investigated the photovoltaic performance of trimethylsulfonium lead triiodide (TMSPbI3) based PSCs and their moisture stability both experimentally and theoretically. The results revealed that TMSPbI3 exhibited a relatively large optical band gap (Eg = 2.32 eV) and high absorption coefficient (α = 2.30 × 104 cm−1 at 500 nm) with a hexagonal one-dimensional crystal structure. The PSCs with a device structure of FTO/c-TiO2/m-TiO2/TMSPbI3/CuSCN/Au exhibited a power conversion efficiency (PCE) of 2.22% with no hysteresis in the I–V curve, and high moisture stability at ambient temperature (25 ± 3 °C, ca. 50% relative humidity) with a PCE loss of only ca. 4.6% after 500 h. This result could be attributed to the absence of the hydrogen bonding interaction of TMS+ with water molecules, leading to the effective stabilization of TMSPbI3 compared to MAPbI3 and FAPbI3, verified by density functional theory calculations.

In this study, we report a new BODIPY-based design, called the cross-conjugated design, that takes advantage of the α- and β-position functionalization of the BODIPY core. After synthesis, and compared to a more standard BODIPY dye, using similar functional groups and based on a horizontal design, called h-BOD, the new cross-conjugated BODIPY dye (cc-BOD) exhibits clearly the highest conjugation and light harvesting properties. Consequently, when used as photosensitizers in dye-sensitized solar cells (DSSCs), an impressive improvement of power conversion efficiency (PCE) has been observed, with a PCE of 6.02% with broad incident photon to current conversion efficiency (IPCE) for cc-BOD, compared to only 3.7% for h-BOD. Moreover, by co-sensitizing a DSSC with the two complementary absorbing dyes h-BOD and cc-BOD, we further improved the PCE up to 6.2%.

Dye sensitized solar cells (DSSCs) were co-sensitized with three custom molecularly engineered organic dyes containing butyloxyl chain induced dye (Y1), boron dipyrromethene (bodipy) dye (TP2A), and squaraine (SQ) ring configured dye (HSQ4). The individual power conversion efficiencies of the DSSCs sensitized with Y1, TP2A and HSQ4 sensitizers were 3.44%, 4.26% and 5.78%, respectively. Co-sensitized TP2A + HSQ4 dyes at a 2 : 1 molar ratio showed an efficiency of 7.02%. Further addition of Y1 dye with optimal TP2A + HSQ4 increased the VOC from 0.580 V to 0.605 V. The co-sensitized Y1 + TP2A + HSQ4 based DSSCs showed a new optimal efficiency (η) of 7.48%. This is the highest efficiency recorded for DSSCs based on co-sensitization of triple organic dyes. Intensity modulated photovoltage spectroscopy further confirms the longer lifetime of co-sensitized Y1 + TP2A + HSQ4 compared to that of each individual TP2A and HSQ4 and co-sensitized TP2A + HSQ4 dye.