Operando studies reveal active Cu nanograins for CO2 electroreduction.

Carbon dioxide electroreduction facilitates the sustainable synthesis of fuels and chemicals1. Although Cu enables CO2-to-multicarbon product (C2+) conversion, the nature of the active sites under operating conditions remains elusive2. Importantly, identifying active sites of high-performance Cu nanocatalysts necessitates nanoscale, time-resolved operando techniques3-5. Here, we present a comprehensive investigation of the structural dynamics during the life cycle of Cu nanocatalysts. A 7 nm Cu nanoparticle ensemble evolves into metallic Cu nanograins during electrolysis before complete oxidation to single-crystal Cu2O nanocubes following post-electrolysis air exposure. Operando analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy shows the presence of metallic Cu nanograins under CO2 reduction conditions. Correlated high-energy-resolution time-resolved X-ray spectroscopy suggests that metallic Cu, rich in nanograin boundaries, supports undercoordinated active sites for C-C coupling. Quantitative structure-activity correlation shows that a higher fraction of metallic Cu nanograins leads to higher C2+ selectivity. A 7 nm Cu nanoparticle ensemble, with a unity fraction of active Cu nanograins, exhibits sixfold higher C2+ selectivity than the 18 nm counterpart with one-third of active Cu nanograins. The correlation of multimodal operando techniques serves as a powerful platform to advance our fundamental understanding of the complex structural evolution of nanocatalysts under electrochemical conditions.

Unraveling the Mechanism of Ammonia Electrooxidation by Coupled Differential Electrochemical Mass Spectrometry and Surface-Enhanced Infrared Absorption Spectroscopic Studies.

Ammonia electrooxidation has received considerable attention in recent times due to its potential application in direct ammonia fuel cells, ammonia sensors, and denitrification of wastewater. In this work, we used differential electrochemical mass spectrometry (DEMS) coupled with attenuated total reflection-surface-enhanced infrared absorption (ATR-SEIRA) spectroscopy to study adsorbed species and solution products during the electrochemical ammonia oxidation reaction (AOR) on Pt in alkaline media, and to correlate the product distribution with the surface ad-species. Hydrazine electrooxidation, hydroxylamine electrooxidation/reduction, and nitrite electroreduction on Pt have also been studied to enhance the understanding of the AOR mechanism. NH3, NH2, NH, NO, and NO2 ad-species were identified on the Pt surface with ATR-SEIRA spectroscopy, while N2, N2O, and NO were detected with DEMS as products of the AOR. N2 is formed through the coupling of two NH ad-species and then subsequent further dehydrogenation, while the dimerization of HNOad leads to the formation of N2O. The NH-NH coupling is the rate-determining step (rds) at high potentials, while the first dehydrogenation step is the rds at low potentials. These new spectroscopic results about the AOR and insights could advance the search and design of more effective AOR catalysts.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Tyrosine kinase inhibitor-induced hypothyroidism: mechanism and clinical implications.

INTRODUCTION: Since the first experimentally proven tyrosine kinase inhibitor (TKI) imatinib was introduced in the clinical setting, TKIs have attracted widespread attention because of their remarkable therapeutic effects and improvement of survival rates. TKIs are small-molecule, multi-target, anti-cancer agents that target different tyrosine kinases and block downstream signaling. ADVERSE REACTIONS AND CONCERNS: However, with in-depth research on TKI drugs, the adverse reactions-for example, thyroid dysfunction-have become a concern and thus have attracted the attention of numerous researchers. Thyroid dysfunction, especially hypothyroidism, that occurs in high incidence during TKI therapy has a close relationship with treatment efficacy, but the mechanism of TKI-induced thyroid dysfunction is obscure. DISCUSSION: This review discusses the epidemiology, possible mechanisms, and clinical significance of hypothyroidism in cancer patients treated with TKI.

Identifying Adsorbed OH Species on Pt and Ru Electrodes with Surface-Enhanced Infrared Absorption Spectroscopy through CO Displacement.

OH adspecies are involved in numerous electrocatalytic reactions, such as CO, H2, methanol, and ethanol oxidation and oxygen reduction reactions, as a reaction intermediate and/or reactant. In this work, we have, for the first time, identified the OH stretching band of OH adspecies on Pt, Ru, and Pt/Ru electrodes with surface-enhanced infrared absorption spectroscopy (SEIRAS) in a flow cell through potential modulation and CO displacement. We found that while Ru had a relatively constant OH coverage at potentials between 0.1 and 0.8 V, Pt had a maximum OH coverage at 0.6 V in 0.1 M HClO4 and 0.7 V in 0.1 M KOH. CO oxidation kinetics on Ru were sluggish, although adsorbed OH appeared on Ru at very low potentials. Binary Pt/Ru electrodes promote CO oxidation through a synergistic effect in which Ru promotes OH adsorption and Pt catalyzes the reaction between the CO and OH adspecies. In addition, water coadsorbed with CO at Ru sites of Pt/Ru also plays an important role. These new spectroscopic results about OH adspecies could advance the understanding of the mechanism of fuel cell related electrocatalysis.

Adsorbed Enolate as the Precursor for the C-C Bond Splitting during Ethanol Electrooxidation on Pt.

Ethanol is a promising alternative fuel to methanol for direct alcohol fuel cells. However, the complete electrooxidation of ethanol to CO2 involves 12 electrons and C-C bond splitting so that the detailed mechanism of ethanol decomposition/oxidation remains elusive. In this work, a spectroscopic platform, combining SEIRA spectroscopy with DEMS, and isotopic labeling were employed to study ethanol electrooxidation on Pt under well-defined electrolyte flow conditions. Time- and potential-dependent SEIRA spectra and mass spectrometric signals of volatile species were simultaneously obtained. For the first time, adsorbed enolate was identified with SEIRA spectroscopy as the precursor for C-C bond splitting during ethanol oxidation on Pt. The C-C bond rupture of adsorbed enolate led to the formation of CO and CHx ad-species. Adsorbed enolate can also be further oxidized to adsorbed ketene at higher potentials or reduced to vinyl/vinylidene ad-species in the hydrogen region. CHx and vinyl/vinylidene ad-species can be reductively desorbed only at potentials below 0.2 and 0.1 V, respectively, or oxidized to CO2 only at potentials above 0.8 V, and thus they poison Pt surfaces. These new mechanistic insights will help provide design criteria for higher-performing and more durable electrocatalysts for direct ethanol fuel cells.

Uncovering the molecular mechanisms of Fructus Choerospondiatis against coronary heart disease using network pharmacology analysis and experimental pharmacology.

Fructus Choerospondiatis (FC), a Mongolian medicine, was mainly used in Mongolian medical theory for the treatment of coronary heart disease (CHD). Nonetheless, the main components and mechanisms of action of FC in the treatment of coronary artery disease have not been studied clearly. AIM OF THE STUDY: The aim of this study is to identify the components of FC and analyze the pathways affected by the targets of these components to probe into the potential mechanisms of action of FC on coronary heart disease. MATERIALS AND METHODS: Identification of compounds in FC employing high performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (HPLC-QTOF-MS) method, then further investigate the network pharmacology and molecular docking to obtain potential targets and elucidate the potential mechanism of action of FC in the therapy of CHD. Experimental validation was established to verify the mechanism of FC in vitro. RESULTS: 21 FC components were identified and 65 overlapping targets were gained. In addition, these ingredients regulated AMPK and PPAR signaling pathway by 65 target genes including IL6, AKT1 and PPARg, etc. Molecular docking displayed that the binding ability of the key target PPARg to FC components turned out to be better. Experimental validation proved that FC treatment decreased the expression of PPARg (p < 0.05) compare with model group, which may be involved in the PPAR signaling pathway. CONCLUSIONS: This study was the first to elucidate the mechanism of action of components of FC for the treatment of CHD using network pharmacology. It alleviated CHD by inhibiting the expression of PPARg to attenuate hypoxia/reoxygenation injury, and the results give a basis for elucidating the molecular mechanism of action of FC for the treatment of coronary heart disease.

Isoindigo-Based Dual-Acceptor Conjugated Polymers Incorporated Conjugation Length and Intramolecular Charge Transfer for High-Efficient Photothermal Conversion.

Photothermal tumor therapy (PTT) and photoacoustic imaging (PA) have emerged as promising noninvasive diagnostic and therapeutic approaches for cancer treatment. However, the development of efficient PTT agents with high photostability and strong near-infrared (NIR) absorption remains challenging. This study synthesizes three isoindigo-based dual-acceptor conjugated polymers (CPs) (P-IIG-TPD, P-IIG-DPP, and P-IIG-EDOT-BT) via a green and nontoxic direct arylation polymerization (DArP) method and characterizes their optical, electrochemical, and NIR photothermal conversion properties. By incorporating two acceptors into the backbone, the resulting polymers exhibit enhanced photothermal conversion efficiency (PCE) due to improved synergy among conjugation length, planarity, and intramolecular charge transfer (ICT). The nanoparticles (NPs) of P-IIG-EDOT-BT and P-IIG-DPP have a uniform size distribution around 140 nm and exhibit remarkable NIR absorption at 808 nm. In addition, P-IIG-EDOT-BT and P-IIG-DPP NPs exhibit high PCEs of 62% and 78%, respectively. This study promotes the molecular design of CPs as NIR photothermal conversion materials and provides guidance for the development of novel dual-acceptor CPs for tumor diagnosis and treatment.

Oxidative Stability Matters: A Case Study of Palladium Hydride Nanosheets for Alkaline Fuel Cells.

Pd-based electrocatalysts are considered to be a promising alternative to Pt in anion-exchange membrane fuel cells (AEMFCs), although major challenges remain. Most of the Pd-based electrocatalysts developed for the sluggish oxygen reduction reaction (ORR) have been exclusively evaluated by rotating disk electrode (RDE) voltammetry at room temperature, rather than in membrane electrode assemblies (MEAs), making it challenging to apply them in practical fuel cells. We have developed a series of carbon-supported novel PdHx nanosheets (PdHx NS), which displayed outstanding ORR performance in room-temperature RDE tests. Specifically, a sample synthesized at 190 °C displayed a mass activity of 0.67 A mg-1 and a specific activity of 1.07 mA cm-2 at 0.95 V vs RHE, representing the highest reported value among Pd-based ORR electrocatalysts in alkaline media and higher than Pt-based catalysts reported in the literature. Furthermore, we employed PdHx NS and commercial Pd/C as model catalysts to systematically study the effects of temperature on their ORR activity in RDE measurements and subsequently evaluated their performance in MEA testing. Our observations indicate/demonstrate how oxidative stability affected the ORR performance of Pd-based electrocatalysts, which provided some critical insights into future ORR catalyst development for alkaline fuel cell applications.

Intercepting Hydrogen Evolution with Hydrogen-Atom Transfer: Electron-Initiated Hydrofunctionalization of Alkenes.

Hydrogen-atom transfer mediated by earth-abundant transition-metal hydrides (M-Hs) has emerged as a powerful tool in organic synthesis. Current methods to generate M-Hs most frequently rely on oxidatively initiated hydride transfer. Herein, we report a reductive approach to generate Co-H, which allows for canonical hydrogen evolution reactions to be intercepted by hydrogen-atom transfer to an alkene. Electroanalytical and spectroscopic studies provided mechanistic insights into the formation and reactivity of Co-H, which enabled the development of two new alkene hydrofunctionalization reactions.

The mechanism underlying arsenic-induced PD-L1 upregulation in transformed BEAS-2B cells.

Chronic exposure to arsenic promotes lung cancer. Human studies have identified immunosuppression as a risk factor for cancer development. The immune checkpoint pathway of Programmed cell death 1 ligand (PD-L1) and its receptor (programmed cell death receptor 1, PD-1) is the most studied mechanism of immunosuppression. We have previously shown that prolonged arsenic exposure induced cell transformation of BEAS-2B cells, a human lung epithelial cell line. More recently our study further showed that arsenic induced PD-L1 up-regulation, inhibited T cell effector function, and enhanced lung tumor formation in the mice. In the current study, using arsenic-induced BEAS-2B transformation as a model system we investigated the mechanism underlying PD-L1 up-regulation by arsenic. Our data suggests that Lnc-DC, a long non-coding RNA, and signal transducer and activator of transcription 3 (STAT3) mediates PD-L1 up-regulation by arsenic.

New insights into methanol and formic acid electro-oxidation on Pt: Simultaneous DEMS and ATR-SEIRAS study under well-defined flow conditions and simulations of CO spectra.

Methanol and formic acid electro-oxidation on Pt has been studied under well-defined flow conditions by a spectroscopic platform that combines differential electrochemical mass spectrometry (DEMS) and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The volatile soluble products from methanol and formic acid oxidation on Pt have been detected by DEMS, while adsorbed intermediates have been identified with ATR-FTIR spectroscopy. Besides CO2 and methylformate, which were detected by DEMS, other non-volatile soluble intermediates such as formaldehyde and formic acid were also generated during methanol oxidation on Pt. Besides water adsorption bands, linearly bonded CO, bridge-bonded CO, adsorbed formate, adsorbed formic acid, and adsorbed CHO bands were observed by ATR-FTIR spectroscopy during methanol and formic acid oxidation on Pt. Formic acid adsorption suppressed the formate and water adsorption. Our results suggest that formate could be an inactive adsorbed species, rather than an active intermediate, for both methanol and formic acid oxidation. Pb modification of Pt significantly enhanced formic acid oxidation through the direct pathway due to the third-body effect and electronic effects. Formic acid oxidation took place mainly at Pb modified low-coordinated defect sites at low potentials. Formic acid decomposition to form adsorbed CO occurred only in the hydrogen region, and Pb modification also slightly enhanced the successive oxidation of adsorbed CO. A double-peak infrared band was observed for linearly bound CO on the Pt film and was simulated with the Fresnel equations and Bruggeman effective medium theory.

Methanol Oxidation at Platinum in Alkaline Media: A Study of the Effects of Hydroxide Concentration and of Mass Transport.

The hydroxide ion concentration dependence of the methanol oxidation reaction at Pt was studied using microelectrode voltammetry and rotating disk electrode voltammetry. Both methods suggest that the rate of methanol oxidation is limited by hydroxide mass transport at low hydroxide concentrations, while it is inhibited by hydroxide adsorption at high concentrations. It was possible to shift from the transport-limited regime to the inhibitory regime by varying the bulk concentration of hydroxide or by varying mass transport to the electrode. Rotating ring-disk electrode voltammetry was employed to qualitatively assess changes in the diffusion layer pH. The results indicated a decrease in the surface pH during methanol oxidation, as expected, but also that the pH reached a steady state during hydroxide transport limited methanol oxidation.

Regression Analysis and Comparison of Economic Parameters with Different Light Index Models under Various Constraints.

Economic globalization is developing more rapidly than ever before. At the same time, economic growth is accompanied by energy consumption and carbon emissions, so it is particularly important to estimate, analyze and evaluate the economy accurately. We compared different nighttime light (NTL) index models with various constraint conditions and analyzed their relationships with economic parameters by linear correlation. In this study, three indices were selected, including original NTL, improved impervious surface index (IISI) and vegetation highlights nighttime-light index (VHNI). In the meantime, all indices were built in a linear regression relationship with gross domestic product (GDP), employed population and power consumption in southeast China. In addition, the correlation coefficient R2 was used to represent fitting degree. Overall, comparing the regression relationships with GDP of the three indices, VHNI performed best with the value of R2 at 0.8632. For the employed population and power consumption regression with these three indices, the maximum R2 of VHNI are 0.8647 and 0.7824 respectively, which are also the best performances in the three indices. For each individual province, the VHNI perform better than NTL and IISI in GDP regression, too. When taking employment population as the regression object, VHNI performs best in Zhejiang and Anhui provinces, but not all provinces. Finally, for power consumption regression, the value of VHNI R2 is better than NTL and IISI in every province except Hainan. The results show that, among the indices under different constraint conditions, the linear relationships between VHNI and GDP and power consumption are the strongest under vegetation constraint in southeast China. Therefore, VHNI index can be used for fitting analysis and prediction of economy and power consumption in the future.

In Situ X-ray Absorption Spectroscopy of a Synergistic Co-Mn Oxide Catalyst for the Oxygen Reduction Reaction.

Identifying the catalytically active site(s) in the oxygen reduction reaction (ORR), under real-time electrochemical conditions, is critical to the development of fuel cells and other technologies. We have employed in situ synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the synergistic interaction of a Co-Mn oxide catalyst which exhibits impressive ORR activity in alkaline fuel cells. X-ray absorption near edge structure (XANES) was used to track the dynamic structural changes of Co and Mn under both steady state (constant applied potential) and nonsteady state (potentiodynamic cyclic voltammetry, CV). Under steady state conditions, both Mn and Co valences decreased at lower potentials, indicating the conversion from Mn(III,IV) and Co(III) to Mn(II,III) and Co(II), respectively. Rapid X-ray data acquisition, combined with a slow sweep rate in CV, enabled a 3 mV resolution in the applied potential, approaching a nonsteady (potentiodynamic) state. Changes in the Co and Mn valence states were simultaneous and exhibited periodic patterns that tracked the cyclic potential sweeps. To the best of our knowledge, this represents the first study, using in situ XAS, to resolve the synergistic catalytic mechanism of a bimetallic oxide. Strategies developed/described herein can provide a promising approach to unveil the reaction mechanism for other multimetallic electrocatalysts.

Colorimetric detection of Ba2+, Cd2+ and Pb2+ based on a multifunctionalized Au NP sensor.

In this work, we developed a colorimetric method for the detection of three kinds of ions with one kind of detection reagent. In detail, gold nanoparticles (Au NPs) multifunctionalized with 3-mercaptonicotinic acid and 4-aminobenzo-18-crown-6 (3-MPA-abc) were prepared and used as a colorimetric sensor for the simple and rapid detection of Ba2+, Cd2+ and Pb2+ ions. After adding Ba2+/Cd2+/Pb2+, the oxygen atom in the crown ether cavity and the carboxyl group of 3-mercaptopropionic acid can react with Ba2+/Cd2+/Pb2+ to form coordination bonds, resulting in the aggregation of the functionalized Au NPs and the color change of Au NP solution. The LOD of the colorimetric sensor for Ba2+/Cd2+/Pb2+ is 20 nM, 20 nM and 50 nM by the naked eye, respectively. A good linear relationship (R2 = 0.9984, R2 = 0.9917, R2 = 0.9934) between the absorbance ratio and Ba2+/Cd2+/Pb2+ concentrations indicates that our Au NP based colorimetric sensor can be used for the quantitative assay of Ba2+/Cd2+/Pb2+, and this detection method was successfully applied in the detection of Ba2+/Cd2+/Pb2+ in real environmental samples.

IrPdRu/C as H2 Oxidation Catalysts for Alkaline Fuel Cells.

H2 oxidation kinetics on Pt in alkaline media are very sluggish, being over 100 times slower than in acidic media, and thus, new and more active H2 oxidation electrocatalysts must be developed in order to enable alkaline exchange membrane fuel cells (AEMFCs). In this Communication, we present a new type of catalysts-carbon-supported IrPdRu nanoparticles-as H2 oxidation catalysts in alkaline media. These catalysts exhibit higher activity than Pt/C and Ir/C catalysts and are also quite stable. In particular, Ir3Ru7/C and Ir3Pd1Ru6/C catalysts are significantly more active and less expensive than Pt/C and Ir/C, and are thus promising new anode catalysts for alkaline fuel cell applications.

An electrochemical quartz crystal microbalance study of a prospective alkaline anion exchange membrane material for fuel cells: anion exchange dynamics and membrane swelling.

A strategy has been devised to study the incorporation and exchange of anions in a candidate alkaline anion exchange membrane (AAEM) material for alkaline fuel cells using the electrochemical quartz crystal microbalance (EQCM) technique. It involves the electro-oxidation of methanol (CH3OH) under alkaline conditions to generate carbonate (CO3(2-)) and formate (HCOO(-)) ions at the electrode of a quartz crystal resonator coated with an AAEM film, while simultaneously monitoring changes in the frequency (Δf) and the motional resistance (ΔR(m)) of the resonator. A decrease in Δf, indicating an apparent mass increase in the film, and a decrease in ΔR(m), signifying a deswelling of the film, were observed during methanol oxidation. A series of additional QCM experiments, in which the effects of CH3OH, CO3(2-), and HCOO(-) were individually examined by changing the solution concentration of these species, confirmed the changes to be due to the incorporation of electrogenerated CO3(2-)/HCOO(-) into the film. Furthermore, the AAEM films were found to have finite anion uptake, validating the expected tolerance of the material to salt precipitation in the AAEM. The EQCM results obtained indicated that HCOO(-) and CO3(2-), in particular, interact strongly with the AAEM film and readily displace OH(-) from the film. Notwithstanding, the anion exchange between CO3(2-)/HCOO(-) and OH(-) was found to be reversible. It is also inferred that the film exhibits increased swelling in the OH(-) form versus the CO3(2-)/HCOO(-) form. Acoustic impedance analysis of the AAEM-film coated quartz resonators immersed in water showed that the hydrated AAEM material exhibits significant viscoelastic effects due to solvent plasticization.

Water oxidation catalysis by Co(II) impurities in Co(III)4O4 cubanes.

The observed water oxidation activity of the compound class Co4O4(OAc)4(Py-X)4 emanates from a Co(II) impurity. This impurity is oxidized to produce the well-known Co-OEC heterogeneous cobaltate catalyst, which is an active water oxidation catalyst. We present results from electron paramagnetic resonance spectroscopy, nuclear magnetic resonance line broadening analysis, and electrochemical titrations to establish the existence of the Co(II) impurity as the major source of water oxidation activity that has been reported for Co4O4 molecular cubanes. Differential electrochemical mass spectrometry is used to characterize the fate of glassy carbon at water oxidizing potentials and demonstrate that such electrode materials should be used with caution for the study of water oxidation catalysis.

CO2 and O2 evolution at high voltage cathode materials of Li-ion batteries: a differential electrochemical mass spectrometry study.

A three-electrode differential electrochemical mass spectrometry (DEMS) cell has been developed to study the oxidative decomposition of electrolytes at high voltage cathode materials of Li-ion batteries. In this DEMS cell, the working electrode used was the same as the cathode electrode in real Li-ion batteries, i.e., a lithium metal oxide deposited on a porous aluminum foil current collector. A charged LiCoO2 or LiMn2O4 was used as the reference electrode, because of their insensitivity to air, when compared to lithium. A lithium sheet was used as the counter electrode. This DEMS cell closely approaches real Li-ion battery conditions, and thus the results obtained can be readily correlated with reactions occurring in real Li-ion batteries. Using DEMS, the oxidative stability of three electrolytes (1 M LiPF6 in EC/DEC, EC/DMC, and PC) at three cathode materials including LiCoO2, LiMn2O4, and LiNi(0.5)Mn(1.5)O4 were studied. We found that 1 M LiPF6 + EC/DMC electrolyte is quite stable up to 5.0 V, when LiNi(0.5)Mn(1.5)O4 is used as the cathode material. The EC/DMC solvent mixture was found to be the most stable for the three cathode materials, while EC/DEC was the least stable. The oxidative decomposition of the EC/DEC mixture solvent could be readily observed under operating conditions in our cell even at potentials as low as 4.4 V in 1 M LiPF6 + EC/DEC electrolyte on a LiCoO2 cathode, as indicated by CO2 and O2 evolution. The features of this DEMS cell to unveil solvent and electrolyte decomposition pathways are also described.