An Energy-Dense, Powerful, Robust Bipolar Zinc-Ferrocene Redox-Flow Battery.

Zinc metal represents a low-cost, high-capacity anode material to develop energy-dense aqueous redox-flow batteries (RFB). However, the energy-storage applications of traditional inorganic Zn halide flow batteries are primarily plagued by the material challenges of traditional halide cathode electrolytes (e.g., bromine), including corrosion, toxicity, and severe crossover. Herein, we report a bipolar zinc-ferrocene salt compound, zinc 1,1'-bis(3-sulfonatopropyl)ferrocene, Zn[Fc(SPr)2 ] (1.80 M solubility or 48.2 Ah L- charge storage capacity)-a robust, energy-dense, bipolar redox-active electrolyte material for RFBs. Zn[Fc(SPr)2 ]-based redox-flow batteries operated at high current densities of up to 200 mA cm-2 and delivered an energy efficiency of up to 81.5 % and a power density of up to 270.5 mW cm-2 . A Zn[Fc(SPr)2 ] flow battery demonstrated an energy density of 20.2 Wh L-1 and displayed nearly 100 % capacity retention for 2000 cycles (1284 h or 53.5 days).

High-performance solar flow battery powered by a perovskite/silicon tandem solar cell.

The fast penetration of electrification in rural areas calls for the development of competitive decentralized approaches. A promising solution is represented by low-cost and compact integrated solar flow batteries; however, obtaining high energy conversion performance and long device lifetime simultaneously in these systems has been challenging. Here, we use high-efficiency perovskite/silicon tandem solar cells and redox flow batteries based on robust BTMAP-Vi/NMe-TEMPO redox couples to realize a high-performance and stable solar flow battery device. Numerical analysis methods enable the rational design of both components, achieving an optimal voltage match. These efforts led to a solar-to-output electricity efficiency of 20.1% for solar flow batteries, as well as improved device lifetime, solar power conversion utilization ratio and capacity utilization rate. The conceptual design strategy presented here also suggests general future optimization approaches for integrated solar energy conversion and storage systems.

Nickel-Catalyzed Electrochemical C(sp3 )-C(sp2 ) Cross-Coupling Reactions of Benzyl Trifluoroborate and Organic Halides*.

Reported here is the redox neutral electrochemical C(sp2 )-C(sp3 ) cross-coupling reaction of bench-stable aryl halides or ß-bromostyrene (electrophiles) and benzylic trifluoroborates (nucleophiles) using nonprecious, bench-stable NiCl2 ⋅glyme/polypyridine catalysts in an undivided cell configuration under ambient conditions. The broad reaction scope and good yields of the Ni-catalyzed electrochemical coupling reactions were confirmed by 50 examples of aryl/ß-styrenyl chloride/bromide and benzylic trifluoroborates. Potential applications were demonstrated by electrosynthesis and late-stage functionalization of pharmaceuticals and natural amino acid modification, and three reactions were run on gram-scale in a flow-cell electrolyzer. The electrochemical C-C cross-coupling reactions proceed through an unconventional radical transmetalation mechanism. This method is highly productive and expected to find wide-spread applications in organic synthesis.

An Efficient Viologen-Based Electron Donor to Nitrogenase.

Nitrogenase catalyzes the reduction of N2 to NH3, supporting all biological nitrogen fixation. Electron donors to this enzyme are ferredoxin or flavodoxin (in vivo) and sodium dithionite (in vitro). Features of these electron donors put a limit on spectrophotometric studies and electrocatalytic applications of nitrogenase. Although it is common to use methyl viologen as an electron donor for many low-potential oxidoreductases, decreased nitrogenase activity is observed with an increasing concentration of methyl viologen, limiting its utility under many circumstances. In this work, we suggest that this concentration-dependent decrease in activity can be explained by the formation of a dimer of the radical cation of methyl viologen (Me2V•+)2 at higher methyl viologen concentrations. In addition, viologens functionalized with positively and negatively charged groups were synthesized and studied using spectroscopy and cyclic voltammetry. A sulfonated viologen derivative, 1,1'-bis(3-sulfonatopropyl)-4,4'-bipyridinium radical {[(SPr)2V•]-}, was found to support full nitrogenase activity up to a mediator concentration of 3 mM, while the positively charged viologen derivative was not an efficient reductant of nitrogenase due to the high standard redox potential. The utility of [(SPr)2V•]- as an electron donor for nitrogenase was demonstrated by a simple, sensitive spectrophotometric assay for nitrogenase activity that can provide accurate values for the specific activity and turnover rate constant under argon. Under N2, the formation of ammonia was confirmed. Because of the observed full activity of nitrogenase and low overpotential, [(SPr)2V•]- should also prove to be valuable for nitrogenase electrocatalysis, including bioelectrosynthetic N2 reduction.

A pH-Neutral, Metal-Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte.

Redox-active anthraquinone molecules represent promising anolyte materials in aqueous organic redox flow batteries (AORFBs). However, the chemical stability issue and corrosion nature of anthraquinone-based anolytes in reported acidic and alkaline AORFBs constitute a roadblock for their practical applications in energy storage. A feasible strategy to overcome these issues is migrating to pH-neutral conditions and employing soluble AQDS salts. Herein, we report the 9,10-anthraquinone-2,7-disulfonic diammonium salt AQDS(NH4 )2 , as an anolyte material for pH-neutral AORFBs with solubility of 1.9 m in water, which is more than 3 times that of the corresponding sodium salt. Paired with an NH4 I catholyte, the resulting pH-neutral AORFB with an energy density of 12.5 Wh L-1 displayed outstanding cycling stability over 300 cycles. Even at the pH-neutral condition, the AQDS(NH4 )2 /NH4 I AORFB delivered an impressive energy efficiency of 70.6 % at 60 mA cm-2 and a high power density of 91.5 mW cm-2 at 100 % SOC. The present AQDS(NH4 )2 flow battery chemistry opens a new avenue to apply anthraquinone molecules in developing low-cost and benign pH-neutral flow batteries for scalable energy storage.

Influence of the backbone of N5-pentadentate ligands on the catalytic performance of Ni(ii) complexes for electrochemical water oxidation in neutral aqueous solutions.

Two N5-chelated nickel complexes displayed decent catalytic activity and good stability for electrochemical water oxidation in phosphate buffer solutions at pH 7, with observed rate constants of 3.06 and 4.62 s-1, which are higher than those reported so far for molecular nickel catalysts in neutral solutions. The results revealed that the rigid backbone of N5-chelating ligands has a positive influence on the activity of the nickel catalysts.

Efficient and Stable Dye-Sensitized Solar Cells Based on a Tetradentate Copper(II/I) Redox Mediator.

The identification of an efficient and stable redox mediator is of paramount importance for commercialization of dye-sensitized solar cells (DSCs). Herein, we report a new class of copper complexes containing diamine-dipyridine tetradentate ligands (L1 = N, N'-dibenzyl- N, N'-bis(pyridin-2-ylmethyl)ethylenediamine; L2 = N, N'-dibenzyl- N, N'-bis(6-methylpyridin-2-ylmethyl)ethylenediamine) as redox mediators in DSCs. Devices constructed with [Cu(L2)]2+/+ redox couple afford an impressive power conversion efficiency (PCE) of 9.2% measured under simulated one sun irradiation (100 mW cm-2, AM 1.5G), which is among the top efficiencies reported thus far for DSCs with copper complex-based redox mediators. Remarkably, the excellent air, photo, and electrochemical stability of the [Cu(L2)]2+/+ complexes renders an outstanding long-term stability of the whole DSC device, maintaining ∼90% of the initial efficiency over 500 h under continuous full sun irradiation. This work unfolds a new platform for developing highly efficient and stable redox mediators for large-scale application of DSCs.

Interfacial Engineering of Perovskite Solar Cells by Employing a Hydrophobic Copper Phthalocyanine Derivative as Hole-Transporting Material with Improved Performance and Stability.

In high-performance perovskite solar cells (PSCs), hole-transporting materials (HTMs) play an important role in extracting and transporting the photo-generated holes from the perovskite absorber to the cathode, thus reducing unwanted recombination losses and enhancing the photovoltaic performance. Herein, solution-processable tetra-4-(bis(4-tert-butylphenyl)amino)phenoxy-substituted copper phthalocyanine (CuPc-OTPAtBu) was synthesized and explored as a HTM in PSCs. The optical, electrochemical, and thermal properties were fully characterized for this organic metal complex. The photovoltaic performance of PSCs employing this CuPc derivative as a HTM was further investigated, in combination with a mixed-ion perovskite as a light absorber and a low-cost vacuum-free carbon as cathode. The optimized devices [doped with 6 % (w/w) tetrafluoro-tetracyano-quinodimethane (F4TCNQ)] showed a decent power conversion efficiency of 15.0 %, with an open-circuit voltage of 1.01 V, a short-circuit current density of 21.9 mA cm-2 , and a fill factor of 0.68. Notably, the PSC devices studied also exhibited excellent long-term durability under ambient condition for 720 h, mainly owing to the introduction of the hydrophobic HTM interlayer, which prevents moisture penetration into the perovskite film. The present work emphasizes that solution-processable CuPc holds a great promise as a class of alternative HTMs that can be further explored for efficient and stable PSCs in the future.