Energy Materials

Electrochemically converting nitrate, widely distributed in industrial wastewater and contaminated water bodies, into ammonia is a promising route for resource recovery and wastewater treatment. Meanwhile, treating harmful algal blooms (HABs) is presented worldwide, are time and resource-consuming, and carries a high CO2 footprint. Rather than considering this carbon and nitrogen-rich biomass as disposable waste, consider it a vast renewable resource. Therefore, this study presents a Fe-dispersed carbon-based catalyst derived from HABs biomass, with a maximum ammonia yield rate of 16449 μg h−1 cm−2 (1.2 mmol h−1 mgcat−1) and NH3 Faradaic efficiency of 87.3%. This catalyst also possessed decent stability with continuous operation over 50 h. Experimental and theoretical calculation results reveal that the Fe-N4 site facilitates electrocatalytic nitrate reduction reaction by reducing the energy barriers of the NO3–to-NH3 pathway. Thus, this strategy of upcycling HABs biomass waste into functional catalysts offers a multipronged approach to renewable and carbon-neutral energy technologies.

Sodium ion insertion plays a critical role in developing robust sodium-ion technologies (batteries and hybrid supercapacitors). Diffusion coefficient values of sodium (DNa+) in tin phosphide between 0.1 V and 2.0 V vs. Na/Na+ are systematically determined by galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS), and potentiostatic intermittent titration technique (PITT). These values range between 4.55 × 10−12 cm2 s−1 and 1.94 × 10−8 cm2 s−1 and depend on the insertion/de-insertion current and the thickness of the electrode materials. Additionally, DNa+ values differ between the first and second cation insertion because of the solid electrolyte interface (SEI) formation. DNa+ vs. insertion potential alters non-linearly in a “W” form due to the strong interactions of Na+ with tin phosphide particles. The results reveal that GITT is a more appropriate electrochemical technique than PITT and EIS for evaluating DNa+ in tin phosphide.

Heavy metal pollution is a key environmental problem. Selectively extracting heavy metals could accomplish water purification and resource recycling simultaneously. Adsorption is a promising approach with a facile process, adaptability for the broad concentration of feed water, and high selectivity. However, the adsorption method faces challenges in synthesizing high-performance sorbents and regenerating adsorbents effectively. FeOOH is an environmentally friendly sorbent with low-cost production on a large scale. Nevertheless, the selectivity behavior and regeneration of FeOOH are seldom studied. Therefore, we investigated the selectivity of FeOOH in a mixed solution of Co2+, Ni2+, and Pb2+ and proposed to enhance the capacity of FeOOH and regenerate it by using external charges. Without charge, the FeOOH electrode shows a Pb2+ uptake capacity of 20 mg/g. After applying a voltage of −0.2/+0.8 V, the uptake capacity increases to a maximum of 42 mg/g and the desorption ratio is 70%–80%. In 35 cycles, FeOOH shows a superior selectivity towards Pb2+ compared with Co2+ and Ni2+, with a purity of 97% ± 3% in the extracts. The high selectivity is attributed to the lower activation energy for Pb2+ sorption. The capacity retentions at the 5th and the 35th cycles are ca. 80% and ca. 50%, respectively, comparable to the chemical regeneration method. With industrially exhausted granular ferric hydroxide as the electrode material, the system exhibits a Pb2+ uptake capacity of 37.4 mg/g with high selectivity. Our work demonstrates the feasibility of regenerating FeOOH by charge and provides a new approach for recycling and upcycling FeOOH sorbent.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2O)2V(µ-O)(PPA)2] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2O)2V(µ-O)(PPA)2] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2O)2V(µ-O)(PPA)2] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2O)2V(µ-O)(PPA)2] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m−1. Temperature-dependent magnetization measurements show that [Cu(H2O)2V(µ-O)(PPA)2] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2O)2V(µ-O)(PPA)2] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2O)2V(µ-O)(PPA)2] shows high electrochemical, and thermal stability.

Due to their high energy density, Li-ion batteries have become indispensable for energy storage in many technical devices. Prussian blue and its analogs are a versatile family of materials. Apart from their direct use as an alkali-ion battery electrode, they are a promising source for templating other compounds due to the presence of carbon, nitrogen, and metallic elements in their structure, ease of synthesis, and high tunability. In this study, homogeneous iron vanadate derivatization from iron vanadium Prussian blue was successfully carried out using an energy efficient infrared furnace utilizing CO2 gas. Iron-vanadate is an inherently unstable electrode material if cycled at low potentials vs. Li/Li+. Several parameters were optimized to achieve a stable electrochemical performance of this derivative, and the effect of surfactants, such as tannic acid, sodium dodecylbenzene sulfonate, and polyvinylpyrrolidone were shown with their role in the morphology and electrochemical performance. While stabilizing the performance, we demonstrate that the type and order of addition of these surfactants are fundamental for a successful coating formation, otherwise they can hinder the formation of PBA, which has not been reported previously. Step-by-step, we illustrate how to prepare self-standing electrodes for Li-ion battery cells without using an organic solvent or a fluorine-containing binder while stabilizing the electrochemical performance. A 400 mA h g−1 capacity at the specific current of 250 mA g−1 was achieved after 150 cycles while maintaining a Coulombic efficiency of 99.2% over an extended potential range of 0.01–3.50 V vs. Li/Li+.

The controlled functionalization of surfaces is of utmost importance for many applications. Surface-initiated living anionic polymerization (SI-LAP) offers a well-adjustable, uniform functionalization without the necessity of metal catalysts for polymerization. However, this technique is rarely studied for functional monomers, such as different methacrylates. The present study investigated the SI-LAP of different methacrylate monomers on porous polystyrene microparticles. Starting with methyl methacrylate (MMA) as the model monomer, the reaction kinetics and the living character of the polymerization at the particles’ surface are discussed. The reaction conditions were transferred to more functional methacrylates, for example, 2-(trimethylsilyloxy)ethyl methacrylate (HEMA-TMS). The functionalization in the particle’s interior enables the preparation of fluorescent particles by applying post-modification protocols of the poly(hydroxyethyl methacrylate) (PHEMA) moieties with fluorescein isothiocyanate. Moreover, ferrocenylmethyl methacrylate (FMMA) polymerization leads to stimuli-responsive particles with an adjustable functional polymer content of 7 to 51%. Electrochemical studies for the latter polymer poly(ferrocenylmethyl methacrylate) (PFMMA) on the surface offered remarkable long-term stability upon addressing the redox responsiveness of the ferrocene moieties over 1000 cycles using electrochemistry. The synthesis strategy enables access to various applications, such as battery anodes, redox-flow batteries, or ion sorbents.

An ontology for the structured storage, retrieval, and analysis of data on lithium-ion battery materials and electrode-to-cell production is presented. It provides a logical structure that is mapped onto a digital architecture and used to visualize, correlate, and make predictions in battery production, research, and development. Materials and processes are specified using a predetermined terminology; a chain of unit processes (steps) connects raw materials and products (items) of battery cell production. The ontology enables the attachment of analytical methods (characterization methods) to items. Workshops and interviews with experts in battery materials and production processes are conducted to ensure that the structure is conformable both for industrial-scale and laboratory-scale data generation and implementation. Raw materials and intermediate products are identified and defined for all steps to the final battery cell. Steps and items are defined based on current standard materials and process chains using terms that are in common use. Alternative structures and the connection of the ontology to other existing ontologies are discussed. The contribution provides a pragmatic, accessible way to unify the storage of materials-oriented lithium-ion battery production data. It aids the linkage of such data with domain knowledge and the automation of data analysis in production and research.

Lithium-ion and sodium-ion batteries (LIBs and SIBs) are crucial in our shift toward sustainable technologies. In this work, the potential of layered boride materials (MoAlB and Mo2AlB2) as novel, high-performance electrode materials for LIBs and SIBs, is explored. It is discovered that Mo2AlB2 shows a higher specific capacity than MoAlB when used as an electrode material for LIBs, with a specific capacity of 593 mAh g−1 achieved after 500 cycles at 200 mA g−1. It is also found that surface redox reactions are responsible for Li storage in Mo2AlB2, instead of intercalation or conversion. Moreover, the sodium hydroxide treatment of MoAlB leads to a porous morphology and higher specific capacities exceeding that of pristine MoAlB. When tested in SIBs, Mo2AlB2 exhibits a specific capacity of 150 mAh g−1 at 20 mA g−1. These findings suggest that layered borides have potential as electrode materials for both LIBs and SIBs, and highlight the importance of surface redox reactions in Li storage mechanisms.

Within the present work, a thermo-responsive ultrafiltration membrane is manufactured based on a polystyrene-block-poly(diethyl acrylamide) block copolymer (BCP). The poly(diethyl acrylamide) block segment features a lower critical solution temperature (LCST) in water, similar to the well-known poly(N-isopropylacrylamide), but having increased biocompatibility and without exhibiting a hysteresis of the thermally induced switching behavior. The BCP is synthesized via sequential “living” anionic polymerization protocols and analyzed by 1H-NMR spectroscopy, size exclusion chromatography, and differential scanning calorimetry. The resulting morphology in the bulk state is investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) revealing the intended hexagonal cylindrical morphology. The BCPs form micelles in a binary mixture of tetrahydrofuran and dimethylformamide, where BCP composition and solvent affinities are discussed in light of the expected structure of these micelles and the resulting BCP membrane formation. The membranes are manufactured using the non-solvent induced phase separation (NIPS) process and are characterized via scanning electron microscopy (SEM) and water permeation measurements. The latter are carried out at room temperature and at 50 °C revealing up to a 23-fold increase of the permeance, when crossing the LCST of the poly(diethyl acrylamide) block segment in water.

Recently, carbon spherogels have been introduced as a novel monolithic aerogel composed of hollow spheres. This material is conveniently obtained via polystyrene (PS) sphere templating. In the present study, we apply a water-soluble titania precursor (titanium(IV) bis(ammonium lactate) to the aqueous sol-gel synthesis based on resorcinol-formaldehyde (RF) to effectively encapsulate titania. In this way, a very high mass loading of up to 59 mass% of titania can be confined strictly to the inside of the hollow carbon spheres. In the final synthesis step, carbonization at 800 °C has three simultaneous effects: Transformation of the RF coating on PS into microporous carbon, PS template removal by decomposition, and formation of titania due to precursor dissociation. A deliberate tuning of the microporous carbon shell, accessibility of the titania, titania amount, and titania's polymorph is further demonstrated by thermal treatment under a carbon dioxide atmosphere. In contrast to non-tuned or TiC-containing carbon spherogels, CO2 activation of the composites results in a three orders of magnitude rise of their photocatalytic activity towards hydrogen evolution reaction, which we evaluate using flow and batch reactors. We further show that this effect is related to the partial etching of the carbon shell, which renders the TiO2 surface accessible to the reactants in the solution and allows for an efficient hole scavenging. Given the simplicity of the hybrid carbon spherogel (HCS) composite fabrication, the high degree of control of their morphological characteristics, and the striking effects of CO2-activation on performance, we believe that our results will contribute to the development of similar carbon-inorganic composites.