Carbon-based materials have emerged as promising anodes for sodium-ion batteries (SIBs) due to the advantages of cost-effectiveness and renewability, whereas the unsatisfactory performance has hampered the commercialization of SIBs. During the past decades, tremendous efforts have been put to enhance the electrochemical performance of SIBs from the perspective of improving the compatibility of electrolytes and electrodes. Hence, a systematic summary of the strategies for tuning electrolytes between hard carbon, graphite, and other structural carbon anodes of SIBs is provided. The formulations and properties of electrolytes with solvents, salts, and additives added, which are closely related to the formation of solid electrolyte interface (SEI) as well as crucial to the reversible capacity, rate capability, and cycling stability of carbon-based anodes, are comprehensively presented. This review is anticipated to provide guidance in future rational tailoring of electrolytes with carbon-based anodes for sodium-ion batteries.

Transition metal-catalyzed, non-enzymatic nitrene transfer (NT) reactions to selectively transform C–H and C=C bonds to new C–N bonds are a powerful strategy to streamline the preparation of valuable amine building blocks. However, many catalysts for these reactions use environmentally unfriendly solvents that include dichloromethane, chloroform, 1,2-dichloroethane and benzene. We developed a high-throughput experimentation (HTE) protocol for heterogeneous NT reaction mixtures to enable rapid screening of a broad range of solvents for this chemistry. Coupled with the American Chemical Society Pharmaceutical Roundtable (ACSPR) solvent tool, we identified several attractive replacements for chlorinated solvents. Selected catalysts for NT were compared and contrasted using our HTE protocol, including silver supported by N-dentate ligands, dinuclear Rh complexes and Fe/Mn phthalocyanine catalysts.

Ammonia produced locally from renewable energy and water electrolysis can be economically competitive with the existing fossil-based global market if its production systems are designed and deployed optimally over the next decade. This transition would reduce the carbon intensity of nitrogen fertilizer by 99 % while ensuring stable and predictable fertilizer prices for the farmers who use this indispensable commodity.

Abstract

Local renewable ammonia production using electrolytic hydrogen is an emerging approach to alleviate emissions attributed to synthetic nitrogen fertilizer production while also insulating against fluctuations in fertilizer prices and mitigating transportation costs and emissions. However, replacing ammonia currently produced using fossil fuels will not be immediate. To this end, we develop a supply chain transition model, which first optimizes the design and hourly operation of new renewable ammonia facilities to minimize production costs and then optimizes the annual installation timing, production scale, and location of these new renewable facilities along with ammonia transportation to meet county resolution demands. The objective is to augment and eventually replace conventional ammonia market imports in an economically competitive manner. We performed a case study for Minnesota's ammonia supply chain and found that a full transition to in-state renewable production by 2032 is optimal. This is incentivized by the U.S. federal government's clean hydrogen production credits. This transition results in 99 % reduction in carbon intensity along with stable supply costs below $475 per metric tonne. New renewable production facilities are an order of magnitude smaller than existing conventional plants. They use both wind and solar resources and operate dynamically to minimize expensive battery and hydrogen storage capacities.

Viologen toxicity: The long-established toxicity of the herbicide methyl-viologen raises concern for deployment of viologen-derivatives as anolyte for neutral aqueous organic redox flow batteries (AORFB) at large scale. Here we show that non-toxic viologen derivatives can be molecularly engineered, holding great promise as safe anolytes for AORFB.

Abstract

Viologen-derivatives are the most widely used redox organic molecules for neutral pH negative electrolyte of redox flow batteries. However, the long-established toxicity of the herbicide methyl-viologen raises concern for deployment of viologen-derivatives at large scale in flow batteries. Herein, we demonstrate the radically different cytotoxicity and toxicology of a series of viologen-derivatives in in vitro assays using model organisms representative of human and environmental exposure, namely human lung carcinoma epithelial cell line (A549) and the yeast Saccharomyces cerevisiae. The results show that safe viologen derivatives can be molecularly engineered, representing a promising family of negolyte materials for neutral redox flow batteries.

The demand for long-term, sustainable, and low-cost battery energy storage systems with high power delivery capabilities for stationary grid-scale energy storage, as well as the necessity for safe lithium-ion battery alternatives, has renewed interest in aqueous zinc-based rechargeable batteries. The Alkaline Ni-Zn rechargeable battery chemistry was identified as a promising technology for sustainable energy storage applications, albeit a considerable investment in academic research, it still fails to deliver the requisite performance. It is hampered by a relatively short-term electrode degradation, resulting in a decreased cycle life. Dendrite formation, parasitic hydrogen evolution, corrosion, passivation, and dynamic morphological growth are all challenging and interrelated possible degradation processes. This Review elaborates on the components of Ni-Zn batteries and their deterioration mechanisms, focusing on the influence of electrolyte additives as a cost-effective, simple, yet versatile approach for regulating these phenomena and extending the battery cycle life. Even though a great deal of effort has been dedicated to this subject, the challenges remain. This highlights that a breakthrough is to be expected, but it will necessitate not only an experimental approach, but also a theoretical and computational one, including artificial intelligence (AI) and machine learning (ML).

Solvent-based CO2 capture consumes significant energy in solvent recovery. To improve energy efficiency, this study investigates CO2 fixation in a solid form through solvation followed by ionic self-assembly–aided precipitation without requiring high energy for solvent regeneration. Based on hypothesis that CO2−3 ions may bind with monovalent metal ions such as Na+, we introduce monovalent Na+ into an aqueous hexane-1,6-diamine solution where CO2 forms carbamate and bicarbonate. Then, Na+ in the solvent act as a seed for ionic self-assembly with diamine carbamate to form an intermediate ionic complex. The recurring chemical reactions lead to an ionic solid formation, which can be easily removed through sedimentation or centrifugation from the aqueous solvent and heated to release the captured CO2. Direct heating of the solids leads to separation of CO2 via decomposition of a solid CO2-diamine-Na molecular aggregate, requiring as low as ~3.4 GJ/t CO2, which is significantly lower than the state-of-the-art polyethyleneimine, CaCO3, and bis-iminoguanidines systems, which require 3.5−10.2 GJ/t CO2. Molecular dynamic simulations support our hypothesis with the use of Na+ to form relatively less stable, yet sufficiently solid, complexes for the least energy-intensive recovery of diamine solvents compared with bivalent carbonate–forming ions.

The mechanism for residual solid (char) formation in lignin depolymerization is proposed. The results demonstrate that the lignin-char is composed of a multiplicate layer of alternate lignin and coke. During the lignin conversion, residual solid is generated from the G and S units in phenolic oligomer via the pathways of alkyl aryl ether rearrangement, α-hydroxyl coupling reaction, and aldol condensation.

Abstract

Current techniques of lignin conversion are challenged by the low carbon utilization efficiency resulting from the severe generation of residual solid (char). Therefore, a better understanding of pathway for char formation is significant and highly desired for lignin valorization. In this work, we propose a fundamental mechanistic insight into char formation in lignin depolymerization, using hydrothermal decomposition as model reaction. The results demonstrate that the char featuring a multi-layer construction of coke and oligomer contains mainly G units, primarily generated from native G-lignin and demethoxylation of S-lignin. Instead, H-lignin contributes to the formation of volatile monophenols. Furthermore, new methylene bridges form between the benzene rings in lignin, which consequently results in the formation of recalcitrant char. Based on these observations, a plausible mechanism for char formation is proposed and verified by the density functional theory calculation.

The crucial ethanol-formed solid-electrolyte interphase (SEI) in Li-nitrogen reduction reaction (NRR) enables ammonia synthesis, even in an ethanol-free electrolyte. The role of ethanol goes beyond acting as a proton shuttle; it facilitates a good SEI and participates in electrolyte transformations.

Abstract

The lithium-mediated nitrogen reduction reaction (Li-NRR) is a promising method for decentralized ammonia synthesis using renewable energy. An organic electrolyte is utilized to combat the competing hydrogen evolution reaction, and lithium is plated to activate the inert N₂ molecule. Ethanol is commonly used as a proton shuttle to provide hydrogen to the activated nitrogen. In this study, we investigate the role of ethanol as a proton shuttle in an electrolyte containing tetrahydrofuran and 0.2 M lithium perchlorate. Particularly designed electrochemical experiments show that ethanol is necessary for a good solid-electrolyte interphase but not for the synthesis of ammonia. In addition, electrochemical quartz crystal microbalance (EQCM) demonstrates that the SEI formation at the onset of lithium plating is of specific importance. Chemical batch synthesis of ammonia combined with real-time mass spectrometry confirms that protons can be shuttled from the anode to the cathode by other species even without ethanol. Moreover, it raises questions regarding the electrochemical nature of Li-NRR. Finally, we discuss electrolyte stability and electrochemical electrode potentials, highlighting the role of ethanol on electrolyte degradation.

Amyloid fibrils from β-lactoglobulin (BLG), lysozyme, and black bean protein were prepared and modified with aminosilane. Then, the amine-functionalized amyloid fibril-templated aerogels were synthesized to capture CO₂ from a dilute atmosphere (~400 ppm CO₂).

Abstract

Climate change caused by excessive CO₂ emissions constitutes an increasingly dire threat to human life. Reducing CO₂ emissions alone may not be sufficient to address this issue, so that the development of emerging adsorbents for the direct capture of CO₂ from the air becomes essential. Here, we apply amyloid fibrils derived from different food proteins as the solid adsorbent support and develop aminosilane-modified amyloid fibril-templated aerogels for CO₂ capture applications. The results indicate that the CO₂ sorption properties of the aerogels depend on the mixing ratio of aminosilane featuring different amine groups and the type of amyloid fibril used. Notably, amine-functionalized β-lactoglobulin (BLG) fibril-templated aerogels show the highest CO₂ adsorption capacity of 51.52 mg (1.17 mmol) CO₂/g at 1 bar CO₂ and 25.5 mg (0.58 mmol) CO₂/g at 400 ppm; similarly, the CO₂ adsorption capacity of chitosan-BLG fibril hybrid aerogels is superior to that of pure chitosan. This study provides a proof-of-concept design for an amyloid fibril-templated hybrid material facilitating applications of protein-based adsorbents for CO₂ capture, including direct air capture.

Molecular hydrogen (H2) is a clean and renewable fuel that has garnered significant interest in the search for alternatives to fossil fuels. Here, we constructed an artificial DNAzyme composed of cobalt-protoporphyrin IX (CoPP) and G-quadruplex DNA, possessing a unique H2Oint ligand between the CoPP and G-quartet planes. We show for the first time that CoPP-DNAzyme catalyzes photo-induced H2 production under anaerobic conditions with a turnover number (TON) of 1229 ± 51 over 12 h at pH 6.05 and 10°C. Compared with free-CoPP, complexation with G-quadruplex DNA resulted in a 4.7-fold increase in H2 production activity. The TON of the CoPP-DNAzyme revealed an optimal acid-base equilibrium with a pKa value of 7.60 ± 0.05, apparently originating from the equilibrium between Co(III)-H– and Co(I) states. Our results demonstrate that the H2Oint ligand can augment and modulate the intrinsic catalytic activity of H2 production catalysts. These systems pave the way to using DNAzymes for H2 evolution in the direct conversion of solar energy to H2 from water.