Redox-active Functional Groups Research Articles

Recent Progress in Covalent Organic Frameworks for Cathode Materials.

Covalent organic frameworks (COFs) are constructed from small organic molecules through reversible covalent bonds, and are therefore considered a special type of polymer. Small organic molecules are divided into nodes and connectors based on their roles in the COF's structure. The connector generally forms reversible covalent bonds with the node through two reactive end groups. The adjustment of the length of the connector facilitates the adjustment of pore size. Due to the diversity of organic small molecules and reversible covalent bonds, COFs have formed a large family since their synthesis in 2005. Among them, a type of COF containing redox active groups such as -C=O-, -C=N-, and -N=N- has received widespread attention in the field of energy storage. The ordered crystal structure of COFs ensures the ordered arrangement and consistent size of pores, which is conducive to the formation of unobstructed ion channels, giving these COFs a high-rate performance and a long cycle life. The voltage and specific capacity jointly determine the energy density of cathode materials. For the COFs' cathode materials, the voltage plateau of their active sites' VS metallic lithium is mostly between 2 and 3 V, which has great room for improvement. However, there is currently no feasible strategy for this. Therefore, previous studies mainly improved the theoretical specific capacity of the COFs' cathode materials by increasing the number of active sites. We have summarized the progress in the research on these types of COFs in recent years and found that the redox active functional groups of these COFs can be divided into six subcategories. According to the different active functional groups, these COFs are also divided into six subcategories. Here, we summarize the structure, synthesis unit, specific surface area, specific capacity, and voltage range of these cathode COFs.

Charge Transfer Kinetics of Redox-Active Microgels.

Polymer microgel particles decorated with redox-active functional groups are a new and promising object for electrochemical applications. However, the process of charge exchange between an electrode and a microgel particle carrying numerous redox-active centers differs fundamentally from charge exchange involving only molecular species. A single act of contact between the microgel and the electrode surface may not be enough to fully discharge the microgel, and partial charge states are to be expected. Understanding the specifics of this process is crucial for the correct analysis of the data obtained from electrochemical experiments with redox-active microgel solutions. In this study, we employed coarse-grained molecular dynamics to investigate in detail the act of charge transfer from a microgel particle to a flat electrode. The simulations take into account both the mobility of functional groups carrying the charge, which depend on the microgel architecture and the charge exchange between the groups, which can accelerate the propagation of charge within the microgel volume. A set of different microgel systems were simulated in order to reveal the impact of their characteristics: fraction of redox-active groups, microgel molecular mass, cross-linker content, cross-linking topology, and solvent quality. We have found trends in microgel composition leading to the most efficient charge transfer kinetics. The obtained results would be useful for understanding experimental results and for optimizing the design of redox-active microgel particles aimed at faster discharge rates.

An Organic Molecular Cathode Composed of Naphthoquinones Bridged by Organodisulfide for Rechargeable Lithium Battery.

Organic electrodes that embrace multiple electron transfer and efficient redox reactions are desirable for green energy storage batteries. Here, a novel organic electrode material is synthesized, i.e., 2, 2'-((disulfanediylbis (4, 1-phenylene)) bis(azanediyl)) bis (naphthalene-1, 4-dione) (MNQ), through a simple click reaction between common carbonyl and organosulfur compounds and demonstrate its application potential as a high-performance cathode material in rechargeable lithium batteries. MNQ exhibits the aggregation effect of redox-active functional groups, the advantage of fast reaction kinetics from molecular structure evolution, and the decreased solubility in aprotic electrolytes resulting from intermolecular interactions. As expected, the MNQ electrode exhibits a high initial discharge capacity of 281.2mAhg-1 at 0.5 C, equivalent to 97.9% of its theoretical capacity, and sustains stable long-term cycling performance of over 1000 cycles at 1 C. This work adds a new member to the family of organic electrode materials, providing performance-efficient organic molecules for the design of rechargeable battery systems, which will undoubtedly spark great interest in their applications.

Overcoming the Potential Window-Limited Functional Group Compatibility by Alternating Current Electrolysis.

The functional group compatibility of an electrosynthetic method is typically limited by its potential reaction window. Here, we report that alternating current (AC) electrolysis can overcome such potential window-limited functional group compatibility. Using alkene heterodifunctionalization as a model system, we design and demonstrate a series of AC-driven reactions that add two functional groups sequentially and separately under the cathodic and anodic pulses, including chloro- and bromotrilfuoromethylation as well as chlorosulfonylation. We discovered that the oscillating redox environment during AC electrolysis allows the regeneration of the redox-active functional groups after their oxidation or reduction in the preceding step. As a result, even though redox labile functional groups such as pyrrole, quinone, and aryl thioether fall in the reaction potential window, they are tolerated under AC electrolysis conditions, leading to synthetically useful yields. The cyclic voltammetric study has confirmed that the product yield is limited by the extent of starting material regeneration during the redox cycling. Our findings open a new avenue for improving functional group compatibility in electrosynthesis and show the possibility of predicting the product yield under AC electrolysis from voltammogram features.

Alkalization-induced disintegration increased redox activity of solid humic acids and its soil biogeochemical implications

Solid humic acids (HAsolid) plays a significant role in maintaining soil ecosystem services, especially in alkaline soil. The unique chemical structures and electrochemical properties are the cores that HAsolid works. In this study, the alkalization-induced variations of particle morphology, functional groups and redox activity of HAsolid were investigated and its soil biogeochemical implications were discussed. Atomic force microscopy (AFM) deflection images and zeta potential results showed that alkalization induced disintegration of HAsolid, with particle size reducing to 200 nm when pH value reached 10.0. This result suggested that HAsolid could exist in alkaline soil. AFM-IR along with fluorescence intensity of HAsolid at different pH further proved that the supramolecular aggregation of HAsolid became loose and dispersive with more redox-active functional groups exposure after alkalization, which could lead to HAsolid susceptible to degradation in alkaline soil. Conductivity of HAsolid decreased 42.86 % when pH increased from 5.0 to 10.0, while electron exchange capacity (EEC) of HAsolid increased 45.30 %, indicating the increase of redox activity of HAsolid. Increase of redox activity of HAsolid by alkalization-induced disintegration not only can accelerate organic pollutant degradation via enhancing microbial co-metabolism, but also speed up the organic carbon loss. This study contributes to a better understanding of the role of HAsolid in organic carbon stocks and fluxes of alkaline soils and has great implications for soil biogeochemical process.

High Voltage: The Molecular Properties of Redox-Active Dissolved Organic Matter in Northern High-Latitude Lakes.

Redox-active functional groups in dissolved organic matter (DOM) are crucial for microbial electron transfer and methane emissions. However, the extent of aquatic DOM redox properties across northern high-latitude lakes and their relationships with DOM composition have not been thoroughly described. We quantified electron donating capacity (EDC) and electron accepting capacity (EAC) in lake DOM from Canada to Alaska and assessed their relationships with parameters from absorbance, fluorescence, and ultrahigh resolution mass spectrometry (FT-ICR MS) analyses. EDC and EAC are strongly tied to aromaticity and negatively related to aliphaticity and protein-like content. Redox-active formulae spanned a range of aromaticity, including highly unsaturated phenolic formulae, and correlated negatively with many aliphatic N and S-containing formulae. This distribution illustrates the compositional diversity of redox-sensitive functional groups and their sensitivity to ecosystem properties such as local hydrology and residence time. Finally, we developed a reducing index (RI) to predict EDC in aquatic DOM from FT-ICR MS spectra and assessed its robustness using riverine DOM. As the hydrology of the northern high-latitudes continues to change, we expect differences in the quantity and partitioning of EDC and EAC within these lakes, which have implications for local water quality and methane emissions.

Enhanced electrochemical performance of flexible asymmetric supercapacitor based on novel nanostructured activated fullerene anchored zinc cobaltite

The rational design and development of nanostructured materials having unique structural and superior electrochemical activity is urgently required for achieving ultra-high energy storage performance. In this regard, activated fullerene decorated over zinc cobaltite (A-C60-ZCO) has been synthesized and its performance evaluation was displayed towards supercapacitor application. As synthesized nanocomposite shows the enhanced specific capacitance of 593.2 F/g at a scan rate of 1 mV/S and retained the capacitance of 83.7% till 5000 cycles at a high current density of 8 A/g. The enhanced performance can be attributed to the hybrid nature of the prepared material, where A-C60 enhances the stability and conductivity and the ZCO enhances the charge storage owing to its pseudo capacitive nature. The incorporation of A-C60 immensely improved the specific capacitance and cyclic stability of the nanocomposite by enhancing hydrophilicity, conductivity, ion/electron transport ability, redox active functional groups and electroactive sites. Furthermore, the constructed flexible asymmetric supercapacitor device provided an energy density of 36.43 Wh/kg at a power density of 1681.47 W/kg, with a superior cycling performance of 91.06% capacitance retention after 5000 cycles at 6 A/g. Owing to the impressive electrochemical performance A-C60-ZCO can be considered as the potential candidate for supercapacitor application.

Reduction capacity of humic acid and its association with the evolution of redox structures during composting

The reducing capacity (RC) of compost-derived humic acid (HA) is related to the type and number of redox-active functional moieties in its structure and has a considerable environmental influence on its geochemical redox cycle. Composting treatment can affect the redox-active fractions of organic substances through microbial transformation and degradation. However, the relationship between the RC of compost-derived HA and its fluorescence component and infrared spectra remains unclear. In this study, we assessed the response of the organic reducing capacity (ORC) and inorganic reducing capacity (IRC) of compost-derived HA to the stabilization of organic solid waste materials by analyzing the redox-active functional groups of HA extracted at different composting times. The results demonstrated that the RC of compost-derived HA continuously increased during composting because of the formation of fulvic- and humic-like fluorescent components, which consist of amide, phenolic hydroxyl, quinone, and aromatic groups. Adsorption occurred between HA and FeCit by aliphatic and out-of-plane aromatic CH, which released free hydrogen and increased the Fe-binding site; consequently, ORC was obviously higher than IRC. The results of this study could provide an understanding of the transformation of the fluorescent substances and functional groups that affect redox properties during composting; therefore, this study has considerable significance for exploring the application of compost products.

Simultaneous redox transformation and removal of Cr(Ⅵ) and As(Ⅲ) by polyethyleneimine modified magnetic mesoporous polydopamine nanocomposite: Insights into synergistic effects and mechanisms

Chromium(Ⅵ) and arsenic(Ⅲ) as typical anionic heavy metal pollutants normally coexist in the environment, greatly aggravating their environmental risks and elevating the difficulty of remediation. Here, a novel polyethyleneimine modified magnetic mesoporous polydopamine nanocomposite (Fe3O4 @mesoPDA/PEI) with abundant active functional groups was exploited as the synchronous adsorbent of Cr(Ⅵ) and As(Ⅲ). The results showed that Cr(Ⅵ) and As(Ⅲ) could mutually promote their conversions and adsorptions on Fe3O4 @mesoPDA/PEI. The adsorption mechanisms of Fe3O4 @mesoPDA/PEI were primarily redox chemistry and also involved electrostatic interactions and coordination. Cr(Ⅵ) was mainly reduced by reductive catechol, while As(Ⅲ) was oxidized to As(Ⅴ) by oxidative active substances (e.g., H2O2, •OH, and quinone). Meanwhile, active intermediate (semiquinone radicals) generated during the Cr(Ⅵ) reduction and As(Ⅲ) oxidation could constitute redox microcirculation with Cr(Ⅵ) and As(Ⅲ) to further accelerate redox reactions of Cr(Ⅵ) and As(Ⅲ) on Fe3O4 @mesoPDA/PEI, thereby exhibiting a synergistic effect. Moreover, newly immobilized Cr(Ⅲ) onto Fe3O4 @mesoPDA/PEI became extra active sites for As adsorption through cation bridges and then recovered by magnetic separation in favor of diminishing the environmental hazards of Cr and As. These findings also provide new inspirations for the roles of redox-active functional groups in the remediation of multiple redox-sensitive heavy metals including Cr(Ⅵ) and As(Ⅲ).

Understanding Hydrogen Bonding Effects on the Reversibility and Redox Potential of Redox Organic Molecules in Deep Eutectic Solvents

Deep eutectic solvent (DES) systems offer unique properties as electrolytes for redox flow batteries. They consist of hydrogen bond donor and acceptor pairs and often offer larger electrochemical windows than traditional aqueous electrolytes with lower vapor pressure than other non-aqueous systems like acetonitrile. They can contain a large concentration of charge carries and have the potential to be high energy density electrolytes1. When paired with redox organic species it is possible to tune both the electrolyte and redox actives to obtain desirable electrochemical properties such as the solubility of active species, kinetic and transport behaviors and even thermodynamic properties such as redox potential2. When attempting to understand these behaviors in DES it becomes important to understand the redox organic molecule’s interaction with the hydrogen bond network. For example, it has been show that altering the ratio of hydrogen bond donor to acceptor sites in a molecule can have dramatic effects on its solubility3. Hydrogen bonding between the DES and the redox organic in its varying charge states can dramatically impact many aspects of the electrochemical behavior.This work focuses on interactions that can have apparent effects on the kinetic and thermodynamic behavior of redox organics. We explore several molecules such as viologen derivatives, PTIO and N-methyl-phthalimide, some of which exhibit reversible behavior in both acetonitrile and a choline chloride and ethylene glycol based DES while other do not. Some see a dramatic shift in redox potential while other do not. We correlate these changes in behavior to influences of hydrogen bonding through the use of IR spectroscopy paired with voltammetry. Red shift in the stretching frequencies of redox active functional groups indicates the presence or lack of hydrogen bonding and this is related to changes in voltammetry as ethylene glycol, a hydrogen bond donor, is added to the redox organic in acetonitrile electrolyte system. It was observed that radical/cation reactions such as PTIO/PTIO+ or viologen were unaffected both kinetically and thermodynamically while reactions involving anionic species such as PTIO-/PTIO or N-methyl-phthalimide would either become irreversible or shift potential. This can be observed for PTIO in the accompanying figure where the cation reaction (more positive couple) does not change while the anion reaction (more negative couple) changes potential dramatically. We propose that some anionic species hydrogen bond more strongly at the redox active sites due to their higher electron density at a hydrogen bond critical point. Electron density has been strongly correlated to hydrogen bond strength4 and molecular modeling is being done to determine the comparative hydrogen bond strength of the anion and cation species as well as reversible and irreversible cationic species. These insights can lead to the intelligent design of highly soluble redox species that remain reversible and make use of the full electrochemical window of a given DES. E. L. Smith, A. P. Abbott and K. S. Ryder, Chem. Rev., 114, 11060–11082 (2014).N. S. Sinclair, D. Poe, R. F. Savinell, E. J. Maginn and J. S. Wainright, J. Electrochem. Soc., 168, 020527 (2021).B. Chen, S. Mitchell, N. Sinclair, J. Wainright, E. Pentzer and B. Gurkan, Mol. Syst. Des. Eng., 5, 1147–1157 (2020).G. Gilli and P. Gilli, J. Mol. Struct., 552, 1–15 (2000). Figure 1

Redox-Active Organic Molecules and Modified Graphene-Based Materials As Active Material Composites for Supercapacitor Applications

Green and sustainable energy demand has directed the modern world toward producing clean energy storage devices to cut down fossil fuel consumption. Supercapacitors are energy storage devices that have attracted much attention due to owning outstanding properties. Supercapacitors use two main mechanisms to storge charge: I) electrical double layer II) pseudocapacitance. Graphene-based materials have shown promising performance in supercapacitors due to their high surface area and proper electrical conductivity. One of the challenges of working with graphene is the restacking of the graphene sheets, leading to poor performance and lower capacitance. Studies have used doping graphene with different heteroatoms as one of the techniques to overcome the restacking and enhancement of its electrochemical performance. Moreover, redox-active organic molecules, including anthraquinones, phenols, and phenathrequinones, also can be employed to modify graphene.In this work we develop composite active material structures consisting of modified graphene-based materials and organic molecules containing redox active functional groups to provide pseudo-capacitance capabilities. By combining these materials, specific capacitance values above 600 F/g were obtained (at cyclic voltammetry scan rates of 50 mV/s) along with good capacitance retention following repeated electrochemical cycling. In this presentation we will discuss the influence of synthesis route and processing parameters and the resulting structures and performance of the active supercapacitor materials. By correlating these results, we provide insight into the energy storage mechanisms and durability considerations pertaining to these hybrid materials.

Controlled Synthesis of Mesoporous π-Conjugated Polymer Nanoarchitectures as Anodes for Lithium-Ion Batteries.

Conjugated polymers possess better electron conductivity due to large π-electron conjugated configuration endowing them significant scientific and technological interest. However, the obvious deficiency of active-site underutilization impairs their electrochemical performance. Therefore, designing and engineering π-conjugated polymers with rich redox functional groups and mesoporous architectures could offer new opportunities for them in these emerging applications and further expand their application scopes. Herein, a series of 1,3,5-tris(4-aminophenyl) benzene (TAPB)-based π-conjugated mesoporous polymers (π-CMPs) are constructed by one-pot emulsion-induced interface assembly strategy. Furthermore, co-induced in situ polymerization on 2D interfaces by emulsion and micelles is explored, which delivers sandwiched 2D mesoporous π-CMPs-coated graphene oxides (GO@mPTAPB). Benefiting from specific redox-active functional groups, excellent electron conductivity and a 2D mesoporous conjugated framework, GO@mPTAPB exhibits high capability of accommodating Li+ anions (up to 382mAhg-1 at 0.2Ag-1 ) and outstanding electrochemical stability (87.6% capacity retention after 1000 cycles). The ex situ Raman and impedance spectra are further applied to reveal the high reversibility of GO@mPTAPB. This work will greatly promote the development of advanced π-CMPs-based organic anodes toward energy storage devices.

Effect of TOC Concentration of Humic Substances as an Electron Shuttle on Redox Functional Groups Stimulating Microbial Cr(VI) Reduction.

Humic substances as an electron shuttle play an essential role in the biogeochemistry processes. However, the influence of total organic carbon (TOC) concentrations of humic substances on microbial Cr(VI) reduction remains unclear. In this study, the rates and extents of Cr(VI) reduction by Shewanella oneidensis MR-1 in the presence of Leonardite humic acids (LHA) and Pahokee peat humic acids (PPHA) with different TOC concentrations were evaluated. We found that the enhanced reduction in Cr(VI) was associated with TOC concentrations of 2.5–50 mg C/L of HA samples. The result shows that HA as an electron shuttle impacted both rates and extents of microbial Cr (VI) reduction, which delivered differently in terms of low TOC concentration range of 2.5 to 15 mg C/L and high concentration range of 15–50 mg C/L. The rates of Cr(VI) reduction significantly enhanced in the low TOC concentration range of HA compared to a high concentration range. The highest acceleration rate of Cr(VI) reduction was achieved at 15 mg C/L of HA. The quinone-like fluorophore was responsible for the main redox-active functional groups of HA by the three-dimensional excitation-emission spectroscopy. The fluorescence intensity of quinone-like fluorophore of HA in the low TOC concentration range was positively correlated with its acceleration coefficient, corresponding to the highest microbial Cr(VI) reduction rate obtained in 15 mg C/L of HA. These findings highlighted the effect of the TOC concentration of HA on microbial Cr(VI) reduction processes. It emphasized that the low TOC concentration of HA contributed to the high rates of Cr(VI) reduction, which is critical for better understanding the fate of Cr(VI) and evaluating the effectiveness of Cr(VI) restoration strategies in the future.

Biogenic formation of amorphous carbon by anaerobic methanotrophs and select methanogens.

Elemental carbon exists in different structural forms including graphite, diamond, fullerenes, and amorphous carbon. In nature, these materials are produced through abiotic chemical processes under high temperature and pressure but are considered generally inaccessible to biochemical synthesis or breakdown. Here, we identified and characterized elemental carbon isolated from consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB), which together carry out the anaerobic oxidation of methane (AOM). Two different AOM consortia, ANME-1a/HotSeep-1 and ANME-2a/c/Seep-SRB, produce a black material with similar characteristics to disordered graphite and amorphous carbon. Stable isotope probing studies revealed that the carbon is microbially generated during AOM. In addition, we found that select methanogens also produce amorphous carbon with similar characteristics to the carbon from AOM consortia. Biogenic amorphous carbon may serve as a conductive element to facilitate electron transfer, or redox active functional groups associated with the carbon could act as electron donors and acceptors.

Contribution of redox-active properties of compost-derived humic substances in hematite bioreduction

The compost-derived humic substances (HS) can function as electron mediators for promoting hematite bioreduction because of its redox capacity. Humification process can affect redox capacities of compost-derived HS by changing its intrinsic structure. However, the redox properties of compost-derived HS linking with hematite bioreduction during composting still remain unclear. Herein, we investigated the redox capacities of compost-derived HS, and assessed the responses of the redox capacities to the hematite bioreduction. The result showed that compost-derived HS (i.e., humic acids (HA) and fulvic acids (FA)) were able to accept electrons from Shewanella oneidensis MR-1, and the electron accepting capacity was increased during composting. Furthermore, it could be functioned as electron mediators for promoting the hematite bioreduction, achieving 1.19-2.15 times compared with the control experience. Not only the aromatic structures (quinone) but also the non-quinone structures such as nitrogen- and sulfur-containing functional moieties were served as the redox-active functional groups of compost-derived HS. Our work proved that the aromatic functional groups and the heteroatom structures (especially N) were important to the hematite bioreduction. This study highlights the redox-active properties of compost-derived HS and its impact on the microbial reduction of iron mineral. Redox capacity of compost-derived HS might mitigate the environmental risk of contaminants when the composting production was added into the contaminated soils as low-cost repair materials

Adsorption and catalytic degradation of organic contaminants by biochar: Overlooked role of biochar’s particle size

Biochar (BC) is considered as a promising adsorbent and/or catalyst for the removal of organic contaminants. However, the relationship between the particle size of BC and its adsorption/catalysis performance is largely unclear. We therefore investigated the influence of particle size on the performance of BC pyrolyzed at 300–900 °C in trichloroethylene (TCE) adsorption and persulfate (PS) activation for sulfamethazine (SMT) degradation. The results showed that high-temperature pyrolyzed BC (BC900) presented superior adsorption capacity for TCE and excellent catalytic activity for PS activation to degrade SMT. Compared to 150–250 µm, 75–150 µm and pristine BC900, 0–75 µm BC900 showed the highest TCE adsorption efficiency, which increased by 19.5–62.3%. Similarly, SMT removal by BC900/PS systems also increased from 24.2% to 98.3% with decreasing BC particle size. However, the catalytic activity of BC after grinding was not significantly improved as expected, indicating the properties of biochar was not only controlled by size effect. Characterization measurements proved that small-sized BC tended to have larger specific surface area, more micropores, higher conductivity, rich graphitic domains and surface redox-active functional groups, thus resulting in an enhanced adsorption and catalytic ability of BC.

Covalent double functionalization of graphene oxide for proton conductive and redox-active functions

The covalent double functionalization of graphene oxide (GO) is an effective approach to tune the properties of graphene-like materials. The first step is the ring-opening reaction of epoxides by amines, followed by the second step consisting on the nucleophilic addition reaction of GO hydroxyl groups to an α,β-unsaturated carbonyl compound. The benefit of doubly functionalized GO is to possess different functions, confirmed by measuring proton conductivity and supercapacitor performance. The proton conductivity can be improved by introducing sulfonic acid and redox-active functional groups on GO, while the capacitance for supercapacitor can be increased by introducing two distinct redox-active molecules. The current study evidences that a double functionalization allow to design a multifunctional GO platform as an electrolyte membrane for fuel cells and/or an electrode material for supercapacitors.

Sodium Butylated Hydroxytoluene: A Functional Group Tolerant, Eco-Friendly Base for Solvent-Free, Pd-Catalysed Amination.

NaBHT (sodium 2,6-di-tert-butyl-4-methylphenolate), a strong, but hindered and lipophilic base, has been effectively paired with similarly lipophilic, high-reactivity Pd-NHC (N-heterocyclic carbene) catalysts to produce an ideal combination for performing solvent-free (melt) cross-coupling amination. The mild nucleophilicity of NaBHT, coupled with the anti-oxidant properties of its conjugate acid byproduct, BHT means the process seems to have no functional group incompatibilities. Highly effective coupling of base-sensitive and redox-active functional groups was observed in all cases with only 0.1-0.2 mol percent catalyst. Comparisons using the standard base for this reaction, KOtBu, led to poor couplings or complete degradation in most applications - only NaBHT works.

Insight to Microbial Fe(III) Reduction Mediated by Redox-Active Humic Acids with Varied Redox Potentials.

Redox-active humic acids (HA) are ubiquitous in terrestrial and aquatic systems and are involved in numerous electron transfer reactions affecting biogeochemical processes and fates of pollutants in soil environments. Redox-active contaminants are trapped in soil micropores (<2 nm) that have limited access to microbes and HA. Therefore, the contaminants whose molecular structure and properties are not damaged accumulate in the soil micropores and become potential pollution sources. Electron transfer capacities (ETC) of HA reflecting redox activities of low molecular weight fraction (LMWF, <2.5) HA can be detected by an electrochemical method, which is related to redox potentials (Eh) in soil and aquatic environments. Nevertheless, electron accepting capacities (EAC) and electron donating capacities (EDC) of these LMWF HA at different Eh are still unknown. EDC and EAC of different molecular weight HA at different Eh were analyzed using electrochemical methods. EAC of LMWF at −0.59 V was 12 times higher than that at −0.49 V, while EAC increased to 2.6 times when the Eh decreased from −0.59 V to −0.69 V. Afterward, LMWF can act as a shuttle to stimulate microbial Fe(III) reduction processes in microbial reduction experiments. Additionally, EAC by electrochemical analysis at a range of −0.49–−0.59 V was comparable to total calculated ETC of different molecular weight fractions of HA by microbial reduction. Therefore, it is indicated that redox-active functional groups that can be reduced at Eh range of −0.49–−0.59 are available to microbial reduction. This finding contributes to a novel perspective in the protection and remediation of the groundwater environment in the biogeochemistry process.

Understanding the Role of Slurry Additive Molecular Structure on Modulating the Interfacial Dynamics for Oxide CMP Applications

As feature sizes continue to shrink well beyond the 7-nm node, understanding the delicate balance present in the chemical mechanical planarization (CMP) process is of utmost importance. In order to achieve high through-put and defect-free CMP processes it is critical to develop predictive analytical techniques that directly correlate to macroscopic STI CMP performance metrics (i.e. oxide/nitride removal, defectivity, and dishing/erosion). This work employed a suite of techniques to monitor the CeO2 nanoparticle interfacial redox processes in the presence of structurally diverse rate modulating additives. Specifically, utilizing a UV-Vis spectroscopic technique, the Ce3+/Ce4+ ratio in the presence of different slurry additives was monitored and proved to directly correlate to removal rate performance (i.e. an increase in Ce3+/Ce4+ ratio shows an increase in rate). This finding coupled with the rate of dissolved O2 evacuation and a modified QCM technique determined the mode of interaction/adsorption which validates that the mechanism of oxide removal does not strictly depend on redox capacity, but also depends on the dynamic O2 equilibrium at the CeO2 nanoparticle surface. In this work, the additives selected provide multiple modes of interaction spanning from noncovalent surface adsorbers to redox active functional groups. It was determined that the modulation of oxide removal was directly related to the distribution of interactions (i.e. steric vs redox) and was highly dependent on the slurry additive functionality.