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1. Surface Interrogation of Electrodeposited MnO _x and CaMnO ₃ Perovskites by Scanning Electrochemical Microscopy: Probing Active Sites and Kinetics for the Oxygen Evolution Reaction

   https://doi.org/10.1002/anie.202008052  

   Jin, Zhaoyu; Bard, Allen J. (November 2020, Angewandte Chemie International Edition)

   Abstract Surface interrogation scanning electrochemical microscopy (SI‐SECM) of two electrodeposited manganese‐based electrocatalysts, amorphous MnO_xand perovskite CaMnO₃, was used to investigate the manganese oxidation state relating to the oxygen evolution reaction (OER) under neutral conditions. The results indicate the amounts of Mn^IIIand Mn^IVspecies in MnO_xand CaMnO₃depend on potential. A Mn^Vspecies was identified in both structures during the OER. Time‐delay titration of Mn^Vfurther revealed that MnO_xproduced two types of active sites with different OER reaction rates:k′_fast(MnO_x)=1.21 s⁻¹andk’_slow(MnO_x)=0.24 s⁻¹. In contrast, CaMnO₃perovskites in which the Mn^Vspecies formed at a less positive potential than that in MnO_x, displayed only one kinetic behavior with a faster reaction rate of 1.72 s⁻¹. 

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2. Biochar and zero-valent iron sand filtration simultaneously removes contaminants of emerging concern and Escherichia coli from wastewater effluent

   https://doi.org/10.1007/s42773-023-00240-y  

   Zhu, Linyan; Chattopadhyay, Suhana; Elijah Akanbi, Oluwasegun; Lobo, Steven; Panthi, Suraj; Malayil, Leena; Craddock, Hillary A.; Allard, Sarah M.; Sharma, Manan; Kniel, Kalmia E.; et al (July 2023, Biochar)

   Abstract Advanced treated municipal wastewater is an important alternative water source for agricultural irrigation. However, the possible persistence of chemical and microbiological contaminants in these waters raise potential safety concerns with regard to reusing treated wastewater for food crop irrigation. Two low-cost and environmentally-friendly filter media, biochar (BC) and zero-valent iron (ZVI), have attracted great interest in terms of treating reused water. Here, we evaluated the efficacy of BC-, nanosilver-amended biochar- (Ag-BC) and ZVI-sand filters, in reducing contaminants of emerging concern (CECs),Escherichia coli (E. coli)and total bacterial diversity from wastewater effluent. Six experiments were conducted with control quartz sand and sand columns containing BC, Ag-BC, ZVI, BC with ZVI, or Ag-BC with ZVI. After filtration, Ag-BC, ZVI, BC with ZVI and Ag-BC with ZVI demonstrated more than 90% (> 1 log) removal ofE. colifrom wastewater samples, while BC, Ag-BC, BC with ZVI and Ag-BC with ZVI also demonstrated efficient removal of tested CECs. Lower bacterial diversity was also observed after filtration; however, differences were marginally significant. In addition, significantly (p < 0.05) higher bacterial diversity was observed in wastewater samples collected during warmer versus colder months. Leaching of silver ions occurred from Ag-BC columns; however, this was prevented through the addition of ZVI. In conclusion, our data suggest that the BC with ZVI and Ag-BC with ZVI sand filters, which demonstrated more than 99% removal of both CECs andE. coliwithout silver ion release, may be effective, low-cost options for decentralized treatment of reused wastewater. Graphical Abstract 

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3. Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

   https://doi.org/https://doi.org/10.1016/j.nanoen.2017.12.015  

   Byles, Bryan W.; Cullen, David A.; More, Karren L.; Pomerantseva, Ekaterina (January 2018, Nano energy)

   Hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO2 and todorokite-MnO2. The other two phases have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl2 solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g−1, 44.4 mg g−1, and 43.1 mg g−1 in NaCl, KCl, and MgCl2 solutions, respectively) and high ion removal rates (as large as 0.112 mg g−1 s−1, 0.165 mg g−1 s−1, and 0.164 mg g−1 s−1 in NaCl, KCl, and MgCl2 solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. This work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions. 

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4. Rechargeable Manganese Dioxide||Hard Carbon Lithium Batteries in an Ether Electrolyte

   https://doi.org/10.1149/1945-7111/ad3415  

   Xia, Dawei; Rosenberg, Keith; Li, Yilin; Hu, Anyang; Sun, Chengjun; Li, Luxi; Nordlund, Dennis; Sainio, Sami; Huang, Haibo; Lin, Feng (March 2024, Journal of The Electrochemical Society)

   Earth-abundant, cost-effective electrode materials are essential for sustainable rechargeable batteries and global decarbonization. Manganese dioxide (MnO₂) and hard carbon both exhibit high structural and chemical tunability, making them excellent electrode candidates for batteries. Herein, we elucidate the impact of electrolytes on the cycling performance of commercial electrolytic manganese dioxide in Li chemistry. We leverage synchrotron X-ray analysis to discern the chemical state and local structural characteristics of Mn during cycling, as well as to quantify the Mn deposition on the counter electrode. By using an ether-based electrolyte instead of conventional carbonate electrolytes, we circumvent the formation of a surface Mn(II)-layer and Mn dissolution from Li_xMnO₂. Consequently, we achieved an impressive ∼100% capacity retention for MnO₂after 300 cycles at C/3. To create a lithium metal-lean full cell, we introduce hard carbon as the anode which is compatible with ether-based electrolytes. Commercial hard carbon delivers a specific capacity of ∼230 mAh g⁻¹at 0.1 A g⁻¹without plateau, indicating a surface-adsorption mechanism. The resulting manganese dioxide||hard carbon full cell exhibits stable cycling and high Coulombic efficiency. Our research provides a promising solution to develop cost-effective, scalable, and safe energy storage solutions using widely available manganese oxide and hard carbon materials. 

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5. Aluminum-Crosslinked Nanocellulose Scaffolds for Fluoride Removal

   https://doi.org/10.3390/nano14121032  

   Johnson, Ken I; Sharma, Sunil K; Sharma, Priyanka R; Alhamzani, Abdulrahman G; Hsiao, Benjamin S (June 2024, Nanomaterials)

   Anionic carboxylated cellulose nanofibers (CNF) are effective media to remove cationic contaminants from water. In this study, sustainable cationic CNF-based adsorbents capable of removing anionic contaminants were demonstrated using a simple approach. Specifically, the zero-waste nitro-oxidization process was used to produce carboxylated CNF (NOCNF), which was subsequently converted into a cationic scaffold by crosslinking with aluminum ions. The system, termed Al-CNF, is found to be effective for the removal of fluoride ions from water. Using the Langmuir isotherm model, the fluoride adsorption study indicates that Al-CNF has a maximum adsorption capacity of 43.3 mg/g, which is significantly higher than that of alumina-based adsorbents such as activated alumina (16.3 mg/g). The selectivity of fluoride adsorption in the presence of other anionic species (nitrate or sulfate) by Al-CNF at different pH values was also evaluated. The results indicate that Al-CNF can maintain a relatively high selectivity towards the adsorption of fluoride. Finally, the sequential applicability of using spent Al-CNF after the fluoride adsorption to further remove cationic contaminant such as Basic Red 2 dye was demonstrated. The low cost and relatively high adsorption capacity of Al-CNF make it suitable for practical applications in fluoride removal from water. 

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