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1.
Nat Commun ; 15(1): 3354, 2024 Apr 18.
Article in English | MEDLINE | ID: mdl-38637529

ABSTRACT

The discovery of Mn-Ca complex in photosystem II stimulates research of manganese-based catalysts for oxygen evolution reaction (OER). However, conventional chemical strategies face challenges in regulating the four electron-proton processes of OER. Herein, we investigate alpha-manganese dioxide (α-MnO2) with typical MnIV-O-MnIII-HxO motifs as a model for adjusting proton coupling. We reveal that pre-equilibrium proton-coupled redox transition provides an adjustable energy profile for OER, paving the way for in-situ enhancing proton coupling through a new "reagent"- external electric field. Based on the α-MnO2 single-nanowire device, gate voltage induces a 4-fold increase in OER current density at 1.7 V versus reversible hydrogen electrode. Moreover, the proof-of-principle external electric field-assisted flow cell for water splitting demonstrates a 34% increase in current density and a 44.7 mW/cm² increase in net output power. These findings indicate an in-depth understanding of the role of proton-incorporated redox transition and develop practical approach for high-efficiency electrocatalysis.

2.
J Colloid Interface Sci ; 666: 276-284, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38603871

ABSTRACT

CO2 electrochemistry has been considered as a promising cathode reaction for energy storage due to its high theoretical energy density, high electrochemical potential, and ability to fix CO2. However, the low efficiency and poor reversibility of Li-CO2 evolution significantly impede the applications of Li-CO2 batteries. Herein, first-principles calculations were employed to investigate the 21 M1M2N4C dual-atom catalysts and explore the catalytic mechanism for the Li-CO2 evolution reaction. Among these dual-atom catalysts, the MoMoN4C shows the highest adsorption interaction with CO2 due to its high d-center and d-p orbital coupling. The effects of dual-atom sites on the catalytic activities and selectivities were investigated by searching the possible reaction pathways toward the battery-discharging processes in the ether electrolyte with the help of implicit constant electrode potential simulations. The compared results show that the Li-CO2 discharging process was limited by the rate-determining reactions involving *Li + CO2 → *LiCO2 and *LiC2O4@ + Li+ + e- → *CO + Li2CO3, and these processes on graphene are relatively sluggish due to the low onset potential range of -2 to -2.36 V vs. SHE. By contrast, The optimized onset potentials of -1.15 to -1.31 V vs. SHE were obtained at the MoMoN4C active site. Furthermore, the MoMoN4C active site shows a lower energy barrier for the decomposition of *Li2CO3 than the pure graphene, which reveals the MoMoN4C active site with excellent CO2 activation ability can reduce the polarization of the discharging reactions and energy barrier for the CO bond cleavage. This work provides deep insight into the Li-CO2 evolution mechanisms and guides the design of advanced dual-atom catalysts for highly reversible Li-CO2 batteries.

3.
Small ; : e2311741, 2024 Mar 12.
Article in English | MEDLINE | ID: mdl-38470196

ABSTRACT

Hydrogen (H2 ) has emerged as a highly promising energy carrier owing to its remarkable energy density and carbon emission-free properties. However, the widespread application of H2 fuel has been limited by the difficulty of storage. In this work, spontaneous electrochemical hydrogen production is demonstrated using hydrazine (N2 H4 ) as a liquid hydrogen storage medium and enabled by a highly active Co catalyst for hydrazine electrooxidation reaction (HzOR). The HzOR electrocatalyst is developed by a self-limited growth of Co nanoparticles from a Co-based zeolitic imidazolate framework (ZIF), exhibiting abundant defective surface atoms as active sites for HzOR. Notably, these self-limited Co nanoparticles exhibit remarkable HzOR activity with a negative working potential of -0.1 V (at 10 mA cm-2 ) in 0.1 m N2 H4 /1 m KOH electrolyte. Density functional theory (DFT) calculations are employed to validate the superior performance of low-coordinated Co active sites in facilitating HzOR. By taking advantage of the potential difference between HzOR and the hydrogen evolution reaction (HER), a novel HzOR||HER electrochemical system is developed to spontaneously produce H2 without external energy input. Overall, the work offers valuable guidance for developing active HzOR catalyst. The novel HzOR||HER electrochemical system represents a promising and innovative solution for energy-efficient hydrogen production.

4.
Sci Total Environ ; 916: 170123, 2024 Mar 15.
Article in English | MEDLINE | ID: mdl-38232842

ABSTRACT

In this study, a rainfall simulation device was employed to investigate the response mechanism of soil leachate and disinfection by-products formation potential (DBPsFP) to extreme precipitation events. The results revealed that the aromaticity of dissolved organic matter (DOM) and the concentration of hydrophobic DOM containing aromatic carbon groups in leachate decreased with rising temperature. The humification degree of DOM decreased at 25 °C (99 mm/h), while the humification degree and protein-like level of DOM increased under high temperatures droughts (45 °C and 65 °C). Higher temperatures resulted in the leach of more microbial-derived humus and low molecular phenolic compounds from soil and broadened the range of molecular weight distribution. Increasing temperature increased DBPsFP and DBPs species and caused the precursors of haloacetic acids (HAAs) in leachate to become more hydrophobic, while the precursors of trihalomethanes (THMs) became more hydrophilic. Most importantly, the increased temperature attenuated the rainfall-mediated dilution of organic pollutant concentration, and temperature has a more significant effect than extreme rainfall in DOM abundance and the formation potential (or species) of DBPs. The results help to better understand the impact of climate change on the physicochemical processes of water quality.

5.
ACS Nano ; 18(6): 5068-5078, 2024 Feb 13.
Article in English | MEDLINE | ID: mdl-38289162

ABSTRACT

Solid-state batteries based on lithium metal anodes are expected to meet safety challenges while maintaining a high energy density. One major challenge lies in the fast interface degradation between the electrolyte and the lithium metal. Herein, we propose a quasi-3D interphase on a garnet solid-state electrolyte (SSE) by introducing lithiophilic nanotrenches. The nanotrenches created by the lithiophilic nanowire array can induce the superfilling of lithium metal into the nanotrenches, resulting in a low interfacial resistance (4 Ω cm2). Moreover, the embedded lithium metal anode optimizes the lithium deposition/stripping behavior not limited at the Li-SSE interface (∼1-10 nm) but extended into the bulk lithium anode (∼10 µm), realizing a high critical current density of 1.8-2.0 mA cm-2 at room temperature (RT). The embedded lithium metal anode is further applied in Li||LiFePO4 solid-state batteries, demonstrating a high reversible areal capacity of ∼3.0 mAh cm-2 at RT.

6.
Angew Chem Int Ed Engl ; 63(9): e202318063, 2024 Feb 26.
Article in English | MEDLINE | ID: mdl-38190839

ABSTRACT

The aqueous zinc-ion battery is promising as grid scale energy storage device, but hindered by the instable electrode/electrolyte interface. Herein, we report the lean-water ionic liquid electrolyte for aqueous zinc metal batteries. The lean-water ionic liquid electrolyte creates the hydrophobic tri-layer interface assembled by first two layers of hydrophobic OTF- and EMIM+ and third layer of loosely attached water, beyond the classical Gouy-Chapman-Stern theory based electrochemical double layer. By taking advantage of the hydrophobic tri-layer interface, the lean-water ionic liquid electrolyte enables a wide electrochemical working window (2.93 V) with relatively high zinc ion conductivity (17.3 mS/cm). Furthermore, the anion crowding interface facilitates the OTF- decomposition chemistry to create the mechanically graded solid electrolyte interface layer to simultaneously suppress the dendrite formation and maintain the mechanical stability. In this way, the lean-water based ionic liquid electrolyte realizes the ultralong cyclability of over 10000 cycles at 20 A/g and at practical condition of N/P ratio of 1.5, the cumulated areal capacity reach 1.8 Ah/cm2 , which outperforms the state-of-the-art zinc metal battery performance. Our work highlights the importance of the stable electrode/electrolyte interface stability, which would be practical for building high energy grid scale zinc-ion battery.

7.
Sci Total Environ ; 912: 169054, 2024 Feb 20.
Article in English | MEDLINE | ID: mdl-38052386

ABSTRACT

N-nitrosodiethylamine (NDEA), which is the most toxic nitrosamine among the 9 detected species, has been widely detected in drinking water. Amines containing diethylamine (DEA) groups in the structure would generate NDEA during the disinfection processes. The aim of this study was to evaluate the feasibility of reducing NDEA formation from a commonly used dithiocarbamate pesticide sodium diethyldithiocarbamate (DEDTC) in subsequent chlorination and chloramination by pre-ozonation. The results demonstrated that NDEA could be generated directly during ozonation, its amounts increased from 0 to 14.34 µg/L with increasing ozone dosages (0-4 mg/L), which was higher than that chlorination (2.68 µg/L) and chloramination (4.91 µg/L) when the initial concentration of DEDTC was 20 µM. Pre-ozonation significantly raised NDEA formation from 2.68 to15.32 µg/L in subsequent chlorination; and that from 4.91 to 9.54 µg/L during subsequent chloramination processes. The addition of •OH scavenger tert-butanol (tBA) increased the production of NDEA from 8.14 to 20.80 µg/L during ozonation, and that from 6.76 to17.98 µg/L in O3/HClO process, 8.74 to 17.33 µg/L in O3/NH2Cl process. Except for NO3- and CO32-, most of the co-existing substances promoted NDEA generation from DEDTC under disinfection conditions. Based on the results of Gaussian theory calculations, GC/MS and UPLC-Q-TOFMS analysis, the influencing mechanisms of pre-ozonation on NDEA generation in the subsequent disinfection process were proposed. In addition, not only acute/chronic toxicity calculation but also luminescent bacteria test was performed to assess the possibility of pre-ozonation on the risk control of DEDTC. The research results fill a gap in the control of NDEA pollution and help to develop a safer ozone oxidation technology.


Subject(s)
Ozone , Water Pollutants, Chemical , Water Purification , Halogenation , Diethylnitrosamine , Feasibility Studies , Disinfection/methods , Ozone/analysis , Water Purification/methods , Water Pollutants, Chemical/analysis
8.
ACS Nano ; 17(21): 21604-21613, 2023 Nov 14.
Article in English | MEDLINE | ID: mdl-37903235

ABSTRACT

TiO2 is a widely recognized intercalation anode material for lithium-ion batteries (LIBs), yet its practical capacity is kinetically constrained due to sluggish lithium-ion diffusion, leading to a lithiation number of less than 1.0 Li+ (336 mAh g-1). Here, the growth of TiO2 crystallites is restrained by integrating Si into the TiO2 framework, thereby enhancing the charge transfer and creating additional active sites potentially residing at grain boundaries for Li+ storage. This strategy is corroborated by the expanded redox range of Ti, as thoroughly demonstrated via synchrotron radiation-based X-ray spectroscopy and Cs-corrected electron microscopy. Consequently, when deployed for lithium storage, the tailored material achieves an extraordinarily high reversible capacity of 559 mAh g-1, 116% of the theoretical maximum of 483 mAh g-1 calculated based on all active species, while simultaneously retaining superior rate capability and robust cycling stability. This work offers fresh perspectives on the revitalization of traditional electrode materials to achieve enhanced capacities.

9.
J Am Chem Soc ; 145(41): 22456-22465, 2023 Oct 18.
Article in English | MEDLINE | ID: mdl-37802095

ABSTRACT

Zinc metal batteries are strongly hindered by water corrosion, as solvated zinc ions would bring the active water molecules to the electrode/electrolyte interface constantly. Herein, we report a sacrificial solvation shell to repel active water molecules from the electrode/electrolyte interface and assist in forming a fluoride-rich, organic-inorganic gradient solid electrolyte interface (SEI) layer. The simultaneous sacrificial process of methanol and Zn(CF3SO3)2 results in the gradient SEI layer with an organic-rich surface (CH2OC- and C5 product) and an inorganic-rich (ZnF2) bottom, which combines the merits of fast ion diffusion and high flexibility. As a result, the methanol additive enables corrosion-free zinc stripping/plating on copper foils for 300 cycles with an average coulombic efficiency of 99.5%, a record high cumulative plating capacity of 10 A h/cm2 at 40 mA/cm2 in Zn/Zn symmetrical batteries. More importantly, at an ultralow N/P ratio of 2, the practical VO2//20 µm thick Zn plate full batteries with a high areal capacity of 4.7 mAh/cm2 stably operate for over 250 cycles, establishing their promising application for grid-scale energy storage devices. Furthermore, directly utilizing the 20 µm thick Zn for the commercial-level areal capacity (4.7 mAh/cm2) full zinc battery in our work would simplify the manufacturing process and boost the development of the commercial zinc battery for stationary storage.

10.
J Hazard Mater ; 460: 132461, 2023 Oct 15.
Article in English | MEDLINE | ID: mdl-37677972

ABSTRACT

The slow reduction of Cu(II) into Cu(I) through peracetic acid (PAA) heavily limited the widespread application of Cu(II)/PAA system. Herein, hydroxylamine (HA) was proposed to boost the oxidative capacity of Cu(II)/PAA system by facilitating the redox cycle of Cu(I)/Cu(II). HA/Cu(II)/PAA system was quite rapid in the removal of diclofenac within a broad pH range of 4.5-9.5, with a 10-fold increase in the removal rate of diclofenac compared with the Cu(II)/PAA system at an optimal initial pH of 8.5. Results of UV-Vis spectra, electron paramagnetic resonance, and alcohol quenching experiments demonstrated that CH3C(O)O•, CH3C(O)OO•, Cu(III), and •OH were involved in HA/Cu(II)/PAA system, while CH3C(O)OO• was verified as the predominant reactive species of diclofenac elimination. Different from previously reported Cu-catalyzed PAA processes, CH3C(O)OO• mainly generated from the reaction of PAA with Cu(III) rather than CH3C(O)O• and •OH. Four possible elimination pathways for diclofenac were proposed, and the acute toxicity of treated diclofenac solution with HA/Cu(II)/PAA system significantly decreased. Moreover, HA/Cu(II)/PAA system possessed a strong anti-interference ability towards the commonly existent water matrix. This research proposed an effective strategy to boost the oxidative capacity of Cu(II)/PAA system and might promote its potential application, especially in copper-contained wastewater.

11.
Nanoscale Adv ; 5(16): 4182-4190, 2023 Aug 08.
Article in English | MEDLINE | ID: mdl-37560427

ABSTRACT

Thermally induced oxygen release is an intrinsic structural instability in layered cathodes, which causes thermal runaway issues and becomes increasingly critical with the continuous improvement in energy density. Furthermore, thermal runaway events always occur in electrochemically aged cathodes, where the coupling of the thermal and electrochemical effect remains elusive. Herein, we report the anomalous segregation of cobalt metal in an aged LiCoO2 cathode, which is attributed to the local exposure of the high-energy (100) surface of LiCoO2 and weak interface Co-O dangling bonds significantly promoting the diffusion of Co. The presence of the LCO-Co interface severely aggregated the oxygen release in the form of dramatic Co growth. A unique particle-to-particle oxygen release pathway was also found, starting from the isolated high reduction areas induced by the cycling heterogeneity. This study provides atomistic insight into the robust coupling between the intrinsic structural instability and electrochemical cycling.

12.
Small Methods ; 7(7): e2201664, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37086112

ABSTRACT

Catalysts with FeNC moieties have demonstrated remarkable activity toward oxygen reduction reaction (ORR), but precise synthesis and configuration regulation of FeNC to achieve bi-functional catalytic sites for ORR and oxygen evolution reaction (OER) remain a great challenge. Herein, a pomegranate-like catalyst with optimized FeN4 configuration is designed. The unique framework affords a large surface area for sufficient active site exposure and abundant macroporous channels for mass transport. By twisting chemical bonds, the electronic structure of FeN4 is regulated, and the adsorption/desorption of oxygen species is facilitated. Compared to noble metal-based catalysts (Pt/C+IrO2 ), the optimized FeNC exhibits impressive onset potential (0.96 V versus reversible hydrogen electrode), larger limiting current density (5.85 mA cm-2 ), and better long-term life for ORR, as well as, lower OER overpotential. When integrated into Zn-air batteries, it demonstrates a respectable peak power density (71.6 mW cm-2 ) and ideal cycling stability (30 h), exceeding that of commercial Pt/C+IrO2 . The exploration offers a guideline for designing advanced bi-functional electrocatalysts.

13.
ChemSusChem ; 16(10): e202300067, 2023 May 19.
Article in English | MEDLINE | ID: mdl-36799004

ABSTRACT

To better satisfy the increasing demands for electric vehicles, it is crucial to develop fast-charging lithium-ion batteries (LIBs). However, the fast-charging capability of commercial graphite anodes is limited by the sluggish Li+ insertion kinetics. Herein, we report a synergistic engineering of uniform nano-sized T-Nb2 O5 particles on graphite (Gr@Nb2 O5 ) with C-O-Nb heterointerfaces, which prevents the growth and aggregation of T-Nb2 O5 nanoparticles. Through detailed theoretical calculations and pair distribution function analysis, the stable existence of the heterointerfaces is proved, which can accelerate the electron/ion transport. These heterointerfaces endow Gr@Nb2 O5 anodes with high ionic conductivity and excellent structural stability. Consequently, Gr@10-Nb2 O5 anode, where the mass ratio of T-Nb2 O5 /graphite=10/100, exhibits excellent cyclic stability and incredible rate capabilities, with 100.5 mAh g-1 after 10000 stable cycles at an ultrahigh rate of 20 C. In addition, the synergistic Li+ storage mechanism is revealed by systematic electrochemical characterizations and in situ X-ray diffraction. This work offers new insights to the reasonable design of fast-charging graphite-based anodes for the next generation of LIBs.

14.
Sci Total Environ ; 873: 162355, 2023 May 15.
Article in English | MEDLINE | ID: mdl-36822419

ABSTRACT

This study was to evaluate the feasibility of controlling carcinogenic nitrosodiethylamine (NDEA) formation from greenhouse gas adsorbent 3-diethylaminopropylamine (DEAPA) by pre-O3 in subsequent chlorination/chloramination processes. The result indicated that the NDEA yields (0.4 %) during chlorination was 1.3 times of that during chloramination (0.3 %); pre-oxidation with 4 mg/L O3 significantly cut down its formation; the reduction rates were up to 67.5 and 48.5 %, respectively. OH scavenger greatly augmented the final NDEA amount from 1.86 to 5.05 µg/L during ozonation, while its roles on subsequent processes differed with disinfection methods as well as O3(g) dosages. Most of co-existed substances inhibited NDEA generation, except NO2-, CO32- and SO42-, which slightly promoted during ozonation. Basing on Gaussian calculation, GC/MS and UPLC-Q-TOF-MS analysis, the influencing mechanisms of pre-O3 on NDEA formation in subsequent disinfection processes were proposed. In addition, the calculated toxicity analysis as well as the whole toxicity was applied to evaluate the possibility of pre-O3 on risk control.


Subject(s)
Greenhouse Gases , Ozone , Water Pollutants, Chemical , Water Purification , Disinfection/methods , Diethylnitrosamine , Carcinogens/toxicity , Halogenation , Water Purification/methods , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/analysis
15.
Adv Mater ; 35(14): e2210966, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36649735

ABSTRACT

Increasing the upper cut-off voltage of LiCoO2 (LCO) is one of the most efficient strategies to gain high-energy density for current lithium-ion batteries. However, surface instability is expected to be exaggerated with increasing voltage arising from the high reactivity between the delithiated LCO and electrolytes, leading to serious safety concerns. This work is aimed to construct a physically and chemically stable phosphate-rich cathode-electrolyte interface (CEI) on the LCO particles to mitigate this issue. This phosphate-rich CEI is generated during the electrochemical activation by using fluoroethylene carbonate and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyletherare as the solvents. Both solvents also demonstrate high thermal stability, reducing the intrinsic flammability of the commercial organic electrolyte, thereby eliminating the safety concern in the LCO-based systems upon high-voltage operation. This stable CEI layer on the particle surface can also enhance the surface structure by blocking direct contact between LCO and electrolyte, improving the cycling stability. Therefore, by using the proposed electrolyte, the LCO cathode exhibits a high-capacity retention of 76.1% after 200 cycles at a high cut-off voltage of 4.6 V. This work provides a novel insight into the rational design of high-voltage and safe battery systems by adopting the flame-retardant electrolyte.

16.
J Hazard Mater ; 448: 130833, 2023 04 15.
Article in English | MEDLINE | ID: mdl-36716556

ABSTRACT

As a vital freshwater resource, rainwater is usually stored in water cellars in arid regions to solve the daily drinking water problems of the population. However, the status of disinfection by-products (DBPs) generation in cellar water under intermittent disinfection conditions is unclear. Therefore, we investigated the formation and distribution characteristics of DBPs in cellar water under intermittent disinfection conditions for the first time. The results demonstrated that six categories of DBPs were selected for detection after chlorination, including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs), haloacetonitriles (HANs), halonitromethanes (HNMs), and nitrosamines (NAs), among which HAAs, HKs, and HANs were the major DBPs. Only bromoacetic acid (MBAA), dichloroacetic acid (DCAA), and trichloroacetic acid (TCAA) showed an increasing trend of accumulation as the number of disinfections increased. Meanwhile, the precursor composition was gradually transformed from humic substances to amino acids, and both organic substances were the main precursors of HAAs. The health risk assessment showed that the main carcinogenic and non-carcinogenic risks of cellar water were contributed by NAs and HAAs, respectively, and children are more susceptible to the risks than adults. The best time to drink cellar water is after approximately 12 days of storage, when the total carcinogenic risk is the minimum.


Subject(s)
Disinfectants , Drinking Water , Water Pollutants, Chemical , Water Purification , Child , Humans , Disinfection/methods , Disinfectants/analysis , Water Pollutants, Chemical/analysis , Drinking Water/analysis , Water Supply , Water Purification/methods , Halogenation , Trihalomethanes/analysis
17.
J Hazard Mater ; 444(Pt A): 130205, 2023 02 15.
Article in English | MEDLINE | ID: mdl-36399819

ABSTRACT

Bromide ions (Br-) affected non-brominated nitroso-dimethylamine (NDMA) formation during ozonation, but the mechanism is still unclear. 1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene) di-semicarbazide (TMDS) was chosen to further probe this problem. The results indicated that low levels of Br- (≤20 µM) enhanced NDMA from 3.27 to 7.56 µg/L, while its amount slightly dropped to 6.22 µg/L raising Br- to 100 µM. It was experimentally verified that intermediates 1,1-dimethylsemicarbazide (DMSC) and 1,1-dimethylhydrazine (UDMH) played important roles on promoting NDMA generation, whose contribution rates were 40.2% and 32.2%, respectively. The brominated substances with higher NDMA molar yields were detected. ∙OH reduced NDMA formation without Br-, while it played promotion role with Br-; the corresponding contribution rates were - 26.9% and 29.2%, respectively. No matter with or without Br-, both ∙O2- and lO2 brought a boost to NDMA formation, their contribution ratios were 34.9% and 58.1% without Br-, while raised significantly to 64.6% and 81.5% when Br- existed. Br- not only facilitated NDMA formation, but also benefited the degradation of TMDS. Based on the calculation results and intermediates detected, the influence mechanisms of Br- were proposed. The results would provide theoretical basis and technical guarantee for treating NDMA precursors and bromide co-existing water in the future.


Subject(s)
Dimethylnitrosamine , Ozone , Reactive Oxygen Species , Bromides
18.
Sci Bull (Beijing) ; 67(18): 1882-1889, 2022 Sep 30.
Article in English | MEDLINE | ID: mdl-36546302

ABSTRACT

Aqueous zinc-ion batteries (AZIBs) are promising for large-scale energy storage, but their development is plagued by inadequate cycle life. Here, for the first time, we reveal an unusual phenomenon of cathodic underpotential deposition (UPD) of Zn, which is highly irreversible and considered the origin of the inferior cycling stability of AZIBs. Combining experimental and theoretical simulation approaches, we propose that the UPD process agrees with a two-dimensional nucleation and growth model, following a thermodynamically feasible mechanism. Furthermore, the universality of Zn UPD is identified in systems, including VO2//Zn, TiO2//Zn, and SnO2//Zn. In practice, we propose and successfully implement removing cathodic Zn UPD and substantially mitigate the degradation of the battery by controlling the end-of-discharge voltage. This work provides new insights into AZIBs degradation and brings the cathodic UPD behavior of rechargeable batteries into the limelight.

19.
J Am Chem Soc ; 144(38): 17407-17415, 2022 Sep 28.
Article in English | MEDLINE | ID: mdl-36121645

ABSTRACT

The proton, as the cationic form of the lightest element-H, is regarded as most ideal charge carrier in "rocking chair" batteries. However, current research on proton batteries is still at its infancy, and they usually deliver low capacity and suffer from severe acidic corrosion. Herein, electrochemically activated metallic H1.75MoO3 nanobelts are developed as a stable electrode for proton storage. The electrochemically pre-intercalated protons not only bond directly with the terminal O3 site via strong O-H bonds but also interact with the oxygens within the adjacent layers through hydrogen bonding, forming a hydrogen-bonding network in H1.75MoO3 nanobelts and enabling a diffusion-free Grotthuss mechanism as a result of its ultralow activation energy of ∼0.02 eV. To the best of our knowledge, this is the first reported inorganic electrode exhibiting Grotthuss mechanism-based proton storage. Additionally, the proton intercalation into MoO3 with formation of H1.75MoO3 induces strong Jahn-Teller electron-phonon coupling, rendering a metallic state. As a consequence, the H1.75MoO3 shows an outstanding fast charging performance and maintains a capacity of 111 mAh/g at 2500 C, largely outperforming the state-of-art battery electrodes. More importantly, a symmetric proton ion full cell based on H1.75MoO3 was assembled and delivered an energy density of 14.7 Wh/kg at an ultrahigh power density of 12.7 kW/kg, which outperforms those of fast charging supercapacitors and lead-acid batteries.

20.
J Environ Sci (China) ; 117: 264-275, 2022 Jul.
Article in English | MEDLINE | ID: mdl-35725078

ABSTRACT

Halogenated disinfection byproducts (DBPs) are an unintended consequence of drinking water disinfection, and can have significant toxicity. XAD resins are commonly used to extract and enrich trace levels of DBPs for comprehensive, nontarget identification of DBPs and also for in vitro toxicity studies. However, XAD resin recoveries for complete classes of halogenated DBPs have not been evaluated, particularly for low, environmentally relevant levels (ng/L to low µg/L). Thus, it is not known whether levels of DBPs or the toxicity of drinking water might be underestimated. In this study, DAX-8/XAD-2 layered resins were evaluated, considering both adsorption and elution from the resins, for extracting 66 DBPs from water. Results demonstrate that among the 7 classes of DBPs investigated, trihalomethanes (THMs), including iodo-THMs, were the most efficiently adsorbed, with recovery of most THMs ranging from 50%-96%, followed by halonitromethanes (40%-90%). The adsorption ability of XAD resins for haloacetonitriles, haloacetamides, and haloacetaldehydes was highly dependent on the individual species. The adsorption capacity of XAD resins for haloacetic acids was lower (5%-48%), even after adjusting to pH 1 before extraction. Recovery efficiency for most DBPs was comparable with their adsorption, as most were eluted effectively from XAD resins by ethyl acetate. DBP polarity and molecular weight were the two most important factors that determine their recovery. Recovery of trichloromethane, iodoacetic acid, chloro- and iodo-acetonitrile, and chloroacetamide were among the lowest, which could lead to underestimation of toxicity, particularly for iodoacetic acid and iodo-acetonitrile, which are highly toxic.


Subject(s)
Disinfectants , Drinking Water , Water Pollutants, Chemical , Water Purification , Acetonitriles , Disinfectants/analysis , Disinfectants/toxicity , Disinfection , Halogenation , Iodoacetates , Trihalomethanes/analysis , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicity , Water Purification/methods
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