Most organic dyes synthesized for dye-sensitized solar cells (DSC) use a single linker group to bind to the metal oxide photo-anode. Here we describe the synthesis and testing of two new triphenylamine dyes containing either two carboxylic acids 5-[2-(4-diphenylamino-phenyl)-vinyl]-isophthalic acid (10) or two cyanoacrylic acids (2Z, 2′Z)-3, 3′-(5-((E)-4-(diphenylamino) styryl)-1, 3-phenylene) bis (2-cyanoacrylic acid) (8) as linker groups. Full characterization data are reported for these dyes and their synthetic intermediates. DSC devices have been prepared from these new dyes either by passive or fast dyeing and the dyes have also been tested in co-sensitized DSC devices leading to a PCE (η = 5.4%) for the double cyanoacrylate linker dye (8) co-sensitized with D149. The dye:TiO₂ surface interactions and dye excitations are interpreted using three modelling methods: density functional theory (at 0 K); molecular dynamics (at 298 K); time dependent density functional theory. The modelling results show the preferred orientation of both dyes on an anatase (1 0 1) TiO₂ surface to be horizontal, and both the simulated and experimental absorption spectra of the dye molecules indicate a red shifted band for (8) compared to (10). This is in line with broader light harvesting and J_sc for (8) compared to (10).

Whilst the highest power conversion efficiency (PCE) perovskite solar cell (PSC) devices that have reported to date have been fabricated by high temperature sintering (>500 °C) of mesoporous metal oxide scaffolds, lower temperature processing is desirable for increasing the range of substrates available and also decrease the energy requirements during device manufacture. In this work, titanium dioxide (TiO₂) mesoporous scaffolds have been compared with metal oxide oxidation catalysts: cerium dioxide (CeO₂) and manganese dioxide (MnO₂). For MnO₂, to the best of our knowledge, this is the first time a low energy band gap metal oxide has been used as a scaffold in the PSC devices. Thermal gravimetric analysis (TGA) shows that organic binder removal is completed at temperatures of 350 °C and 275 °C for CeO₂ and MnO₂, respectively. By comparison, the binder removal from TiO₂ pastes requires temperatures >500 °C. CH₃NH₃PbBr₃ PSC devices that were fabricated while using MnO₂ pastes sintered at 550 °C show slightly improved PCE (η = 3.9%) versus mesoporous TiO₂ devices (η = 3.8%) as a result of increased open circuit voltage (V_oc). However, the resultant PSC devices showed no efficiency despite apparently complete binder removal during lower temperature (325 °C) sintering using CeO₂ or MnO₂ pastes.

The global steel industry uses fossil fuels to produce millions of tonnes of iron ore sinter each year. Sintering is an energy-intensive process that fuses iron ore and flux to produce material that balances a high mechanical strength at a sufficient particle size to ensure a macroporous burden in the blast furnace to enable rapid gas flow. As significant CO₂ greenhouse emissions are emitted, the defossilisation of these CO₂ emissions is vital to net-zero carbon targets. Two iterations of a new biomass–coal hybrid fuel (ecoke^®(A) and ecoke^®(B)) were compared with coke breeze and an anthracite coal using oxygen bomb calorimetry, simultaneous thermal analysis (STA) combining thermogravimetry and differential scanning calorimetry, and isoconversional kinetic modelling and pyrolysis–GCMS to study the volatile matter. The calorific values of both ecoke^®(A) and (B) were marginally higher than that of the coke breeze: 27.9 MJ/kg and 27.8 MJ/kg, respectively, compared with 26.5 MJ/kg for the coke breeze. A proximate analysis revealed both ecoke^® samples to have higher volatile matter contents (ca. 12–13%) than the coke breeze (7.4%), but less than the anthracite coal (ca. 14%). The thermogravimetric analysis of the burnout kinetics of the fuels heated up to 1000 °C, at heating rates from 5 to 25 °C/min, showed that that the coke breeze and anthracite coal had higher ignition and burnout temperatures than the ecoke^® samples. Kinetic analysis using the Freidman and Ozawa methods found that the ecoke^® samples showed comparable maximum mass loss rates to the coke breeze but lower activation energies. From these results, both ecoke^® samples have the potential to replace some of the coke breeze in the sintering process or EAF processes to help achieve net zero by offsetting up to 30% of the CO₂ emissions.

We report the synthesis of organometal halide perovskites by milling CH₃NH₃I and PbI₂ directly with an Al₂O₃ scaffold to create hybrid Al₂O₃-CH₃NH₃PbI₃ perovskites, without the use of organic capping ligands that otherwise limit the growth of the material in the three dimensions. Not only does this improve the ambient stability of perovskites in air (100 min versus 5 min for dimethylformamide (DMF)-processed material), the method also uses much fewer toxic solvents (terpineol versus dimethylformamide). This has been achieved by solid-state reaction of the perovskite precursors to produce larger perovskite nanoparticles. The resulting hybrid perovskite–alumina particles effectively improve the hydrophobicity of the perovskite phase whilst the increased thermal mass of the Al₂O₃ increases the thermal stability of the organic cation. Raman data show the incorporation of Al₂O₃ shifts the perovskite spectrum, suggesting the formation of a hybrid 3D mesoporous stack. Laser-induced current mapping (LBIC) and superoxide generation measurements, coupled to thermogravimetric analysis, show that these hybrid perovskites demonstrate slightly improved oxygen and thermal stability, whilst ultra-fast X-ray diffraction studies using synchrotron radiation show substantial (20×) increase in humidity stability. Overall, these data show considerably improved ambient stability of the hybrid perovskites compared to the solution-processed material.

This paper reports studies on the thermal chemistry of the flash pyrolysis (heating rate of 20,000 °C/s up to 800 °C) of non-fossil fuel carbon (NFF-C) waste (or refuse-derived fuel, RDF) in the context of using this as an alternative reductant for blast furnace ironmaking. Gas chromatography–mass spectrometry (GCMS) analysis linked to the pyrolyser was used to simulate the thermal processes that take place during injection in the blast furnace raceway, where material experiences extreme temperature (ca. 1000 °C) over very short residence times (<300 ms). Species identification and qualitative analysis of evolved species generated are reported. Whilst the pyrolyser uses flash heating of a static sample, a drop tube furnace was also employed to study a sample moving rapidly through a pre-heated furnace held at 1000 °C to enable reductant burnout rates to be measured. The overarching aim of this piece of work is to study the suitability of replacing fossil fuel with non-recyclable plastic and paper as blast furnace reductants.