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Organic solar cells utilize an energy-level offset to generate free charge carriers. Although a very small energy-level offset increases the open-circuit voltage, it remains unclear how exactly charge generation is affected. Here we investigate organic solar cell blends with highest occupied molecular orbital energy-level offsets (∆EHOMO) between the donor and acceptor that range from 0 to 300 meV. We demonstrate that exciton quenching at a negligible ∆EHOMO takes place on timescales that approach the exciton lifetime of the pristine materials, which drastically limits the external quantum efficiency. We quantitatively describe this finding via the Boltzmann stationary-state equilibrium between charge-transfer states and excitons and further reveal a long exciton lifetime to be decisive in maintaining an efficient charge generation at a negligible ∆EHOMO. Moreover, the Boltzmann equilibrium quantitatively describes the major reduction in non-radiative voltage losses at a very small ∆EHOMO. Ultimately, highly luminescent near-infrared emitters with very long exciton lifetimes are suggested to enable highly efficient organic solar cells. Donor–acceptor systems with low energy-level offset enable high power efficiency in organic solar cells yet it is unclear what drives charge generation. Classen et al. show that long exciton lifetimes enable efficient exciton splitting and thus generation of free charges while also suppressing voltage losses.

Moisture availability is a strong determinant of decomposition rates in forests worldwide. Climate models suggest that many terrestrial ecosystems are at risk from future droughts, suggesting moisture limiting conditions will develop across a range of forests worldwide. The impacts of increasing drought conditions on forest carbon (C) fluxes due to shifts in organic matter decay rates may be poorly characterised due to limited experimental research. To appraise this question, we conducted a meta-analysis of forest drought experiment studies worldwide, examining spatial limits, knowledge gaps and potential biases. To identify limits to experimental knowledge, we projected the global distribution of forest drought experiments against spatially modelled estimates of (i) future precipitation change, (ii) ecosystem total above-ground C and (iii) soil C storage. Our assessment, involving 115 individual experimental study locations, found a mismatch between the distribution of forest drought experiments and regions with higher levels of future drought risk and C storage, such as Central America, Amazonia, the Atlantic Forest of Brazil, equatorial Africa and Indonesia. Decomposition rate responses in litter and soil were also relatively under-studied, with only 30 experiments specifically examining the potential experimental impacts of drought on C fluxes from soil or litter. We propose new approaches for engaging experimentally with forest drought research, utilising standardised protocols to appraise the impacts of drought on the C cycle, while targeting the most vulnerable and relevant forests.

AbstractThe preparation of nanomaterials for energy applications such as intercalation batteries and materials that can act as substrates for water oxidation is a subject of major interest nowadays. In this work, we report the deposition of Prussian blue (PB) and its cobalt analogue (CoPBA) on mesoporous titania thin films (MTTF) using the successive ionic layer adsorption reaction (SILAR) technique under soft conditions. A bifunctional ligand, 1,10‐phenanthroline‐5,6‐dione (pd), was used to functionalize the titania surface and promote the growth of PB and CoPBA. The resulting PB@MTTF and CoPBA@MTTF nanocomposites were characterized using several techniques and it was determined that PB and CoPBA grow in a controlled and sequential manner, maintaining the mesoporous architecture. Both PB@MTTF and CoPBA@MTTF demonstrated very good electroactive properties, while CoPBA@MTTF exhibited water oxidation capabilities. The flexibility of this PBA@MTTF platform allows the incorporation of any labile transition metal ion or fragment into the structure of the coordination polymer embedded into a mesoporous matrix, opening the door for (photo)electrochemical devices and catalysts.

This review highlights the importance of controlling the crystallization dynamics for the deposition of high-quality photovoltaic perovskite layers on larger-area coatings.

Humic-like substances (HULIS) account for a major redox-active fraction of biomass burning organic aerosols (BBOA). During atmospheric transport, fresh acidic BB-HULIS in droplets and humid aerosols are subject to neutralization and pH-modified aging process. In this study, solutions containing HULIS isolated from wood smoldering emissions were first adjusted with NaOH and NH3 to pH values in the range of 3.6-9.0 and then aged under oxic dark conditions. Evolution of HULIS oxidative potential (OP) and total peroxide content (equivalent H2O2 concentration, H2O2eq) were measured together with the changes in solution absorbance and chemical composition. Notable immediate responses such as peroxide generation, HULIS autoxidation, and an increase in OP and light absorption were observed under alkaline conditions. Initial H2O2eq, OP, and absorption increased exponentially with pH, regardless of the alkaline species added. Dark aging further oxidized the HULIS and led to pH-dependent toxic and chemical changes, exhibiting an alkaline-facilitated initial increase followed by a decrease of OP and H2O2eq. Although highly correlated with HULIS OP, the contributions of H2O2eq to OP are minor but increased both with solution pH and dark aging time. Alkalinity-assisted autoxidation of phenolic compounds and quinoids with concomitant formation of H2O2 and other alkalinity-favored peroxide oxidation reactions are proposed here for explaining the observed HULIS OP and chemical changes in the dark. Our findings suggest that alkaline neutralization of fresh BB-HULIS represents a previously overlooked peroxide source and pathway for modifying aerosol redox-activity and composition. Additionally, these findings imply that the lung fluid neutral environment can modify the OP and peroxide content of inhaled BB-HULIS. The results also suggest that common separation protocols of HULIS using base extraction methods should be treated with caution when evaluating and comparing their composition, absorption, and relative toxicity.

Anaerobic nitrogen removal technologies offer advantages in terms of energy and cost savings over conventional nitrification-denitrification systems. A mathematical model was constructed to evaluate the influence of process operation on the coexistence of nitrite dependent anaerobic methane oxidizing bacteria (n-damo) and anaerobic ammonium oxidizing bacteria (anammox) in a single granule. The nitrite and methane affinity constants of n-damo bacteria were measured experimentally. The biomass yield of n-damo bacteria was derived from experimental data and a thermodynamic state analysis. Through simulations, it was found that the possible survival of n-damo besides anammox bacteria was sensitive to the nitrite/ammonium influent ratio. If ammonium was supplied in excess, n-damo bacteria were outcompeted. At low biomass concentration, n-damo bacteria lost the competition against anammox bacteria. When the biomass loading closely matched the biomass concentration needed for full nutrient removal, strong substrate competition occurred resulting in oscillating removal rates. The simulation results further reveal that smaller granules enabled higher simultaneous ammonium and methane removal efficiencies. The implementation of simultaneous anaerobic methane and ammonium removal will decrease greenhouse gas emissions, but an economic analysis showed that adding anaerobic methane removal to a partial nitritation/anammox process may increase the aeration costs with over 20%. Finally, some considerations were given regarding the practical implementation of the process.