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The search for affordable high performance electrode materials in photoelectrochemical hydrogen production by solar water splitting is an ongoing quest. Hematite is a photoanode material with an electronic band gap suitable for efficient absorption of visible light in a photoelectrochemical cell (PEC). Although its poor electronic structure makes hematite a controversial candidate for PEC, it remains promising because it is an earth abundant, chemically stable and low cost material – necessary prerequisites for PEC to become a competitive cost-efficient solar fuel economy. In addition to reviewing some recent PEC research on hematite and its relevant physical and chemical characteristics, we show how hematite obtained by a low cost synthesis can be refined by hydrothermal treatment and further functionalized by coating with phycocyanin, a light harvesting protein known for photosynthesis in blue-green algae.

AbstractOngoing rapid climate change is predicted to cause local extinction of plant species in mountain regions. However, some plant species could have persisted during Quaternary climate oscillations without shifting their range, despite the limited evidence from fossils. Here, we tested two candidate mechanisms of persistence by comparing the macrorefugia and microrefugia (MR) hypotheses. We used the rare and endemic Saxifraga florulenta as a model taxon and combined ensembles of species distribution models (SDMs) with a high‐resolution paleoclimatic and topographic dataset to reconstruct its potential current and past distribution since the last glacial maximum. To test the macrorefugia hypothesis, we verified whether the species could have persisted in or shifted to geographic areas defined by its realized niche. We then identified potential MR based on climatic and topographic properties of the landscape and applied refined scenarios of MR dynamics and functions over time. Last, we quantified the number of known occurrences that could be explained by either the macrorefugia or MR model. A consensus of two or three SDM techniques predicted absence between 14–10, 3–4 and 1 ka bp, which did not support the macrorefugia model. In contrast, we showed that S. florulenta could have contracted into MR during periods of absence predicted by the SDMs and later re‐colonized suitable areas according to the macrorefugia model. Assuming a limited and realistic seed dispersal distance for our species, we explained a large number of the current occurrences (61–96%). Additionally, we showed that MR could have facilitated range expansions or shifts of S. florulenta. Finally, we found that the most recent and the most stable MR were the ones closest to current occurrences. Hence, we propose a novel paradigm to explain plant persistence by highlighting the importance of supporting functions of MR when forecasting the fate of plant species under climate change.

AbstractThe recent rise in atmospheric methane (CH4) concentrations accelerates climate change and offsets mitigation efforts. Although wetlands are the largest natural CH4 source, estimates of global wetland CH4 emissions vary widely among approaches taken by bottom‐up (BU) process‐based biogeochemical models and top‐down (TD) atmospheric inversion methods. Here, we integrate in situ measurements, multi‐model ensembles, and a machine learning upscaling product into the International Land Model Benchmarking system to examine the relationship between wetland CH4 emission estimates and model performance. We find that using better‐performing models identified by observational constraints reduces the spread of wetland CH4 emission estimates by 62% and 39% for BU‐ and TD‐based approaches, respectively. However, global BU and TD CH4 emission estimate discrepancies increased by about 15% (from 31 to 36 TgCH4 year−1) when the top 20% models were used, although we consider this result moderately uncertain given the unevenly distributed global observations. Our analyses demonstrate that model performance ranking is subject to benchmark selection due to large inter‐site variability, highlighting the importance of expanding coverage of benchmark sites to diverse environmental conditions. We encourage future development of wetland CH4 models to move beyond static benchmarking and focus on evaluating site‐specific and ecosystem‐specific variabilities inferred from observations.

Quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) were used to study zipper and layer-by-layer multilayer assemblies of artificial photosystems based on naphthalenediimides (NDIs) attached to an oligophenylethynyl (OPE-NDI) or p-oligophenyl (POP-NDI) backbone in dry and wet state. For the most interesting OPE-NDI zipper, one obtains for the dry film a monolayer thickness of 1.85 nm and a density of 1.58 g/cm(3), while the wet film has a larger monolayer thickness of 3.6 nm with a water content of 36%. The dry thickness of a monolayer in OPE-NDI zippers corresponds to about one-half of the length of the OPE scaffold in agreement with the proposed structure of the zipper. The low water content of the OPE-NDI films confirms their compact structure. The dry monolayer thickness of the POP-NDI films of 1.45 nm is smaller than that for the OPE-NDI films, which is probably related to a tilt of the POP scaffolds within the adsorbed layer. The POP-NDI films swell in water much more substantially, suggesting a much more open structure. These features are in excellent agreement with the better photophysical performance of the OPE-NDI assemblies when compared to the POP-NDI films.

Facile access to complex systems is crucial to generate the functional materials of the future. Herein, we report self-organizing surface-initiated polymerization (SOSIP) as a user-friendly method to create ordered as well as oriented functional systems on transparent oxide surfaces. In SOSIP, self-organization of monomers and ring-opening disulfide exchange polymerization are combined to ensure the controlled growth of the polymer from the surface. This approach provides rapid access to thick films with smooth, reactivatable surfaces and long-range order with few defects and high precision, including panchromatic photosystems with oriented four-component redox gradients. The activity of SOSIP architectures is clearly better than that of disordered controls.

AbstractA metal‐free organic sensitizer, suitable for the application in dye‐sensitized solar cells (DSSCs), has been designed, synthesized and characterized both experimentally and theoretically. The structure of the novel donor–acceptor–π‐bridge–acceptor (D–A–π–A) dye incorporates a triphenylamine (TPA) segment and 4‐(benzo[c][1,2,5]thiadiazol‐4‐ylethynyl)benzoic acid (BTEBA). The triphenylamine unit is widely used as an electron donor for photosensitizers, owing to its nonplanar molecular configuration and excellent electron‐donating capability, whereas 4‐(benzo[c][1,2,5]thiadiazol‐4‐ylethynyl)benzoic acid is used as an electron acceptor unit. The influences of I3−/I−, [Co(bpy)3]3+/2+ and [Cu(tmby)2]2+/+ (tmby=4,4′,6,6′‐tetramethyl‐2,2′‐bipyridine) as redox electrolytes on the DSSC device performance were also investigated. The maximal monochromatic incident photon‐to‐current conversion efficiency (IPCE) reached 81 % and the solar light to electrical energy conversion efficiency of devices with [Cu(tmby)2]2+/+ reached 7.15 %. The devices with [Co(bpy)3]3+/2+ and I3−/I− electrolytes gave efficiencies of 5.22 % and 6.14 %, respectively. The lowest device performance with a [Co(bpy)3]3+/2+‐based electrolyte is attributed to increased charge recombination.

A synthesis is presented highlighting the importance of hydrologic variables and dynamics to biodiversity patterns. The focus of this paper is the key hydrologic controls crucial towards quantifying the impacts of climate changes on the distribution of species. Specifically, we highlight the hydrologic controls operating on the carrying capacity, niche formation, and dispersal dynamics. This synthesis will facilitate avenues of future research and is connected to issues of major practical importance, such as the integration of the structure of river networks into conservation strategies and the evaluations of the impacts of climate change on biodiversity.