Electron Spin Resonance Measurements Research Articles

Ultrahigh Surface Area Nanoporous Carbons Synthesized via Hypergolic and Activation Reactions for Enhanced CO2 Capacity and Volumetric Energy Density.

We report a family of carbon sorbents synthesized by integrating hypergolics with activation reactions on a templated substrate. The materials design leads to nanoporous carbons with a BET area of 4800 m2 g-1 with an impressive total pore volume of 2.7 cm3 g-1. To the best of our knowledge, this BET area value is the highest reported in the literature. Electron spin resonance (ESR) measurements determined the number of radicals in an effort to provide a mechanistic understanding of the formation of ultrahigh surface area carbons. In combination with XPS, we propose a mechanism based on the synergistic effect between rim-based pentagonal rings and carbon radicals, which we believe can be exploited to produce other highly porous carbons. The CO2 capture capacity of the hyperporous carbon tested under dynamic CO2 capture conditions was ∼1.25 mmol g-1 versus 0.66 mmol g-1 of a conventionally activated carbon under similar conditions. The CO2 capture kinetics were extremely fast and reached 99% of the total capacity within 120 s. Lastly, supercapacitor electrodes deliver a high volumetric energy density of ∼60 W h L-1 and a volumetric power density of 1 kW L-1, which is the highest reported value for activated carbon.

Hydrogen-Bond-Induced Melem Assemblies to Resist Aggregation-Caused Quenching for Ultrasensitive ECL Detection of COVID-19 Antigen.

Nowadays, aggregation-caused quenching (ACQ) of organic molecules in aqueous media seriously restricts their analytical and biomedical applications. In this work, hydrogen bond (H-bond) was utilized to resist the ACQ effect of 2,5,8-triamino-1,3,4,6,7,9,9b-heptaazaphenalene (Melem) as an advanced electrochemiluminescence (ECL) luminophore, whose ECL process was carefully studied in an aqueous K2S2O8 system coupled with electron paramagnetic resonance (EPR) measurements. Notably, the H-bond-induced Melem assemblies (Melem-H) showed 16.6-fold enhancement in the ECL signals as compared to the Melem aggregates (Melem-A), combined by elaborating the enhanced mechanism. On such basis, the effective ECL signal transduction was in situ achieved through the specific recognition of the double-stranded DNA embedded in Melem-H assemblies (Me-dsDNA) with spike protein (SP) of coronavirus disease 2019 (COVID-19). For that, such an ECL biosensor showed a wider linear range (1.0-125.0 pg mL-1) with a lower limit of detection (LOD) down to 0.45 pg mL-1, which also displayed acceptable results in analysis of human nasal swab samples. Therefore, the work provides a distinctive insight on addressing the ACQ effect and broadening the application scope of the organic emitter and offers a simple platform for biomedical detection.

ESR measurement of carbonated hydroxyapatite for dosemeter.

We have examined a dosimetry characteristic of carbonate hydroxyapatite (CO3HAp), which is a dental bone graft material. The purpose of this work is to investigate the reproducibility and stability of radiation-induced radicals on CO3HAp samples and assess the feasibility of using these materials as dosemeters. CO3HAp samples were exposed to gamma rays with dose range from 10 to 10000Gy. The electron spin resonance (ESR) spectra for irradiated samples were measured. Variation of peak-to-peak amplitude of the ESR signal intensity as a function of absorbed dose for CO3HAp was compared with that for alanine dosemeters, suggesting that the CO3HAp sample has a good linear dose response in the range from 10to 10000Gy as well as does the alanine dosemeters.

Continuous-Flow Electron Spin Resonance Measurements of Hydroxyl Radicals Produced during Photocatalytic Water Oxidation

Continuous-Flow Electron Spin Resonance Measurements of Hydroxyl Radicals Produced during Photocatalytic Water Oxidation

Boosting activation of S2O82− by Fe3+-tartaric acid complex for rapid carbamazepine degradation via photo-Fenton mechanism

Activation of S2O82− by Fe2+ is suppressed under non-acidic pH conditions, strongly hindering its application for water purification. To this end, this study reported an efficient photo-Fenton activation of S2O82− by Fe3+-tartaric acid complex at circumneutral pH. The results showed that UVA irradiation induced a rapid photogeneration of Fe2+ from Fe3+-tartaric acid complex at circumneutral pH, by which efficient photo-Fenton activation of S2O82− was obtained to generate sulfate radical (SO4•-), as evidenced by radical quenching study in combination with electron spin resonance measurement. The process efficiency was optimized in terms of the tartaric acid:Fe3+ ratio, Fe3+-tartaric acid complex dosage, S2O82− dosage and UV fluence. Notably, the photo-Fenton catalytic efficiency of Fe3+-tartaric acid (1:1) complex for S2O82− was comparable to the Fe3+-EDDS (1:1) and Fe3+-citric acid (1:1) complexes, and more efficient than the Fe3+-NTA (1:1), Fe3+-EDTA (1:1), Fe3+-oxalic acid (1:1) and Fe3+-malonic acid (1:1) complexes. It is noticed that the process efficiency can be hindered by the presence of humic acid, phytic acid and HCO3−. Nevertheless, almost complete degradation of carbamazepine in actual secondary effluents at environmental relevant concentration was obtained under the optimal conditions of 100 μM Fe3+-tartaric acid (1:1) complex, 2 mM S2O82−, pH 5.0–6.0, 25 °C and UV fluence of 5.0 J cm−2. By considering the promising photo-Fenton catalytic efficiency and environmentally benign manner of Fe3+-tartaric acid complex, it has large potential application for the treatment of emerging micropollutant in water.

Z-scheme heterojunction photocatalyst of LaFeO3@CoS for tetracycline hydrochloride degradation by persulfate activation using visible light

An efficient and stable LaFeO3@CoS Z-scheme heterojunction photocatalyst was prepared through the hydrothermal method (HT). Photocatalytic activity of the LaFeO3@CoS was assessed by activating persulfate under visible light for the degradation of tetracycline (0.1 g/L). Under the condition of 0.06 g/L of KHSO5 (Peroxymonosulfate, PMS), the degradation efficiency of 88.7 % was achieved in 40 min using the 0.02 g/L of developed photocatalyst. The degradation kinetic constants of LaFeO3@CoS were 2.79 and 2.23 times higher than those of LaFeO3 and CoS, respectively. Furthermore, the catalyst exhibited excellent stability over five consecutive degradation cycles. Possible degradation mechanisms and the electron transfer mechanism of the heterojunction formed by the LaFeO3@CoS were investigated by quenching experiments, nitrogen N₂ purging experiments, electron spin resonance (ESR) measurements and corresponding electrochemical analyses. In the LaFeO3@CoS/Vis/PMS system, the Z-scheme charge transfer pathway not only accelerated charge transport efficiency but also effectively spatially separated electrons and holes, enhancing the photocatalytic performance of the photocatalyst. Additionally, the generation of reactive species such as 1O2, O2•−, and SO4• − significantly contributed to the improved degradation efficiency of the present catalyst during the degradation process.

Formation of Radical-like NH Ligand from NH3 at Ambient Conditions Mediated by Dialkyl Rare-Earth Complexes.

Although intensive work on ammonia activation has been carried out in recent decades, generating nitrogen-centered radicals from NH3 under ambient conditions remains quite challenging. In the presented research, the conversion of NH3 to radical-like NH ligand has been achieved by the reactions of a series of dialkyl rare-earth (RE) complexes (1-RE, RE = Tb, Dy, Y, Ho, Er, Yb, and Lu) supported by β-diketiminate ligands with NH3 in n-hexane at room temperature, resulting in the formations of the radical-like μ3-NH ligands containing trinuclear RE complexes (2-RE). The radical-like feature of the μ3-NH ligand was revealed by electron paramagnetic resonance and magnetic measurements, radical trapping experiments, and computational spin density analysis. In addition, H2 was detected to form during the reaction of 1-RE with NH3, indicating that the radical-like μ3-NH ligand was likely to be generated via N-H bond homolysis. Moreover, the solvents and coordination pattern of β-diketiminate ligands are crucial for the formation of the radical-like μ3-NH ligand from NH3. When toluene instead of n-hexane was used in the reaction of 1-RE with NH3, an array of octaamido tetranuclear RE complexes (3-RE) was obtained. The reaction of the dialkyl yttrium complex (4-Y) bearing a modified β-diketiminate ligand, in which the two mesityl substituents are replaced by a 2,6-diisopropylphenyl group and a 2-(dimethylamino)ethyl group, with NH3 in both n-hexane and toluene only yielded a tetranuclear yttrium complex carrying the dianionic closed-shell μ3-NH ligands (5-Y).

Eustigmatophyte model of red-shifted chlorophyll a absorption in light-harvesting complexes

Photosynthetic organisms harvest light for energy. Some eukaryotic algae have specialized in harvesting far-red light by tuning chlorophyll a absorption through a mechanism still to be elucidated. Here, we combined optically detected magnetic resonance and pulsed electron paramagnetic resonance measurements on red-adapted light-harvesting complexes, rVCP, isolated from the freshwater eustigmatophyte alga Trachydiscus minutus to identify the location of the pigments responsible for this remarkable adaptation. The pigments have been found to belong to an excitonic cluster of chlorophylls a at the core of the complex, close to the central carotenoids in L1/L2 sites. A pair of structural features of the Chl a403/a603 binding site, namely the histidine-to-asparagine substitution in the magnesium-ligation residue and the small size of the amino acid at the i-4 position, resulting in a [A/G]xxxN motif, are proposed to be the origin of this trait. Phylogenetic analysis of various eukaryotic red antennae identified several potential LHCs that could share this tuning mechanism. This knowledge of the red light acclimation mechanism in algae is a step towards rational design of algal strains in order to enhance light capture and efficiency in large-scale biotechnology applications.

Research on in-vivo electron paramagnetic resonance spectrum classification and radiation dose prediction based on machine learning

The in-vivo electron paramagnetic resonance (EPR) method can be used for on-site, rapid, and non-invasive detection of radiation dose to casualties after nuclear and radiation emergencies. For in-vivo EPR spectrum analysis, manual labeling of peaks and calculation of signal intensity are often used, which have problems such as large workload and interference by subjective factors. In this study, a method for automatic classification and identification of in-vivo EPR spectra was established using support vector machine (SVM) technology, which can in-batch and automatically identify and screen out invalid spectra due to vibration and dental surface water interference during in-vivo EPR measurements. In this study, a spectrum analysis method based on genetic algorithm optimization neural network (GA-BPNN) was established, which can automatically identify the radiation-induced signals in in-vivo EPR spectra and predict the radiation doses received by the injured. The experimental results showed that the SVM and GA-BPNN spectrum processing methods established in this study could effectively accomplish the automatic spectra classification and radiation dose prediction, and could meet the needs of dose assessment in nuclear emergency. This study explored the application of machine learning methods in EPR spectrum processing, improved the intelligence level of EPR spectrum processing, and would help to enhance the efficiency of mass EPR spectra processing.

Enhancing Photogenerated Radical Pair Properties in Donor-Chromophore-Acceptor Systems for Quantum Information Applications.

We report on new donor-chromophore-acceptor triads BDX-ANI-NDI and BDX-ANI-xy-NDI where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dioxole, the ANI chromophore is 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a p-methoxyaniline (MeOAn) as the donor. BDX•+ has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn•+. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (J) for BDX•+-ANI-NDI•- and BDX•+-ANI-xy-NDI•- at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that BDX•+-ANI-xy-NDI•- has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of J. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.

Use of In-Situ ESR Measurements for Mechanistic Studies of Free Radical Non-Catalytic Thermal Reactions of Various Unconventional Oil Resources and Biomass

The exhaustion of conventional light oils necessitates the shift towards unconventional sources such as biomass, heavy oil, oil shale, and coal. Non-catalytic thermal cracking by a free radical mechanism is at the heart of the upgrading, prior to refining into valuable products. However, thermal pyrolysis is hindered by the formation of asphaltenes, precursors to coke, limiting cracking, causing equipment fouling, and reducing product stability. Free radicals are inherently present in heavy fractions and are generated during thermal processes. This makes these reactive intermediates central to understanding these mechanisms and limiting coking. Electron spin resonance (ESR) spectroscopy facilitates such mechanistic studies. Over the past decade, there has been no review of using in-situ ESR for studying thermal processes. This work begins with a brief description of free radicals’ chain reactions during thermal reactions and the wealth of information ESR provides. We then critically review the literature that uses ESR for mechanistic studies in thermal pyrolysis of biomass, heavy oil, shales, and coal. We conclude that limited literature exist, and more investigations are necessary. The key findings from existing literature are summarized to know the current state of knowledge. We also explicitly highlight the research gaps.

Elaborate construction of a MOF-derived novel morphology Z-scheme ZnO/ZnCdS heterojunction for enhancing photocatalytic H2 evolution and tetracycline degradation

Elaborate construction of novel Z-scheme heterojunction with exceptional morphology derived from metal-organic framework (MOF) have been attracted greatly interest for improving the photocatalytic ability. Herein, a Z-scheme ZnO/ZnCdS heterojunction of rare morphology with ultrathin-nanosheet assembled hierarchical morphology ZnCdS supporting on rich gap ZnO nanospheres were constructed from Zn-based MOF (namely PZH-139) for the first time. This unique feature increased specific surface area, offered abundant mass transport channels and accessible catalytic active sites, accelerated electron migration, which highly elevated photocatalytic property. Furthermore, electron paramagnetic resonance (EPR) measurements and density functional theory (DFT) calculations confirmed the reservation of strong redox capability owing to Z-scheme electron transfer path and the ΔGH* closer to zero of Z-scheme ZnO/ZnCdS system were another two key factors for boosting the photocatalytic activity. As a result, 3-ZnO-700/ZnCdS-160 with optimal morphology showed the best H2 generation performance of 15.43 mmol h−1 g−1 and degradation tetracycline (TC) efficiency of 98.14 %. This work offered a novel and feasible idea for elaborate synthesis of the high-efficiency Z-scheme ZnO/ZnCdS heterojunction with special morphology derived from Zn-MOF.

A bis-Phenolate Carbene-Supported bis-μ-Oxo Iron(IV/IV) Complex with a [FeIV(μ-O)2FeIV] Diamond Core Derived from Dioxygen Activation.

The diiron(II) complex, [(OCO)Fe(MeCN)]2 (1, MeCN = acetonitrile), supported by the bis-phenolate carbene pincer ligand, 1,3-bis(3,5-di-tert-butyl-2-hydroxyphenyl)benzimidazolin-2-ylidene (OCO), was synthesized and characterized by single-crystal X-ray diffraction, 1H nuclear magnetic resonance, infrared (IR) vibrational, ultraviolet/visible/near-infrared (UV/vis/NIR) electronic absorption, 57Fe Mössbauer, X-band electron paramagnetic resonance (EPR) and SQUID magnetization measurements. Complex 1 activates dioxygen to yield the diferric, μ-oxo-bridged complex [(OCO)Fe(py)(μ-O)Fe(O(C═O)O)(py)] (2) that was isolated and fully characterized. In 2, one of the iron-carbene bonds was oxidized to give a urea motif, resulting in an O(CNHC═O)O binding site, while the other Fe(OCO) unit remained unchanged. When the reaction is performed at -80 °C, an intensively colored, purple intermediate is observed (INT, λmax = 570 nm; ε = 5600 mol L-1 cm-1). INT acts as a sluggish oxidant, reacting only with easily oxidizable substrates, such as PPh3 or 2-phenylpropionic aldehyde (2-PPA). The identity of INT can be best described as a dinuclear complex containing a closed diamond core motif [(OCO)FeIV(μ-O)2FeIV(OCO)]. This proposal is based on extensive spectroscopic [UV/vis/NIR electronic absorption, 57Fe Mössbauer, X-band EPR, resonance Raman (rRaman), X-ray absorption, and nuclear resonance vibrational (NRVS)] and computational studies. The conversion of the diiron(II) complex 1 to the oxo diiron(IV) intermediate INT is reminiscent of the O2 activation process in soluble methane monooxygenases (sMMO). Most importantly, the low reactivity of INT supports the consensus that the [FeIV(μ-O)2FeIV] diamond core in sMMO is kinetically inert and needs to open up to terminal FeIV═O cores to react with the strong C-H bonds of methane.

Electron Paramagnetic Resonance Analysis of Hydroquinone Polymerization Catalyzed by Small Laccase

AbstractLaccases are multi‐copper oxidases (MCOs) that oxidize a broad range of substrates while reducing molecular oxygen to water. Although much effort has been made to elucidate the catalytic mechanism of laccases, information about reactive catalytic intermediates during catalysis is not yet fully understood. Herein, hydroquinone (HQ) polymerization catalyzed by prokaryotic small laccase (SLAC) was investigated by electron paramagnetic resonance (EPR) spectroscopy to provide more information on the catalytic mechanism. Briefly, free radical intermediates during the catalysis were investigated by real‐time in situ EPR measurement to monitor the formation and transformation of free radicals. A paramagnetic species was identified which was attributed to a copolymer formed by hydroquinone, benzoquinone, and semiquinone radical. In addition, the low‐temperature EPR spectrum of the trinuclear copper center during catalysis not only revealed tentative rotational motion of the histidine imidazole rings coordinating the TNC upon electron uptake but also provided evidence of the formation of oxygen bridge at TNC during the reaction, represented by the observation of a new type 2 copper component featured larger g// values and smaller A// values. Together, EPR spectroscopic insights into the catalytic intermediates during enzymatic hydroquinone polymerization have extended the knowledge of the biophysical characteristics and catalytic mechanism of SLAC.

Robust resistance switching performance in a Ca3Ti2O7/La0.67Sr0.33MnO3 heterostructure induced by the interface

Ruddlesden–Popper phase oxides, such as Ca3Ti2O7, have been established as hybrid improper ferroelectrics. However, investigations into Ca3Ti2O7 have primarily concentrated on their structural and ferroelectric properties. In this study, we prepared epitaxial Ca3Ti2O7 thin films via magnetron sputtering. Conducting atomic force microscopy was employed to characterize local current variations under an applied bias voltage. Electron paramagnetic resonance measurements of the Ca3Ti2O7/La0.67Sr0.33MnO3 film were conducted to assess its defect characteristics. Interestingly, the Ca3Ti2O7/La0.67Sr0.33MnO3 stacks exhibited remarkable macroscopic resistance switching, with a resistance on/off ratio reaching 100, alongside robust retention (∼2500 s) and endurance (∼2000 cycles) features. Additionally, density functional theory calculations suggest that the resistance switching is attributable to the interface barrier of the Ca3Ti2O7/La0.67Sr0.33MnO3 interface and the efficacy of space charge limitation. This work proposes an avenue for the utilization of Ruddlesden–Popper phase Ca3Ti2O7 in various applications.

Effect of charge-discharge with higher capacitance performance of Ni-substituted CoFe2O4 magnetic nanoparticles for energy storage

In this work, we synthesized NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) magnetic nanoparticles (MNPs) by using ultrasonication-assisted reverse chemical co-precipitation method. The X-ray diffraction (XRD) patterns confirm the single-phase with mixed spinel structure of the NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs with the crystallite size range between 12 nm - 17 nm. The molecular dynamics and oleic acid coated Ni-substituted CoFe2O4 magnetic nanoparticles were confirmed by FTIR measurements. The surface composition of NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs (Ni, Co, Fe and O) and their oxidation states were estimated using X-ray photoelectron spectroscopy. The NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs are spherical in shape and polycrystalline in nature, confirmed by FESEM and HRTEM measurements. The Ni-substituted CoFe2O4 MNPs with higher zeta potential (ζ) from −24 mV to -41 mV with an increase in Ni concentration, signifies the stable colloidal stability due to the electrostatic repulsion between MNPs. The DC magnetization (M-vs-H) measurements reveal the ferrimagnetic behavior of NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs, which suppress the saturation magnetization (MS) from 48.6 emu/g to 5.3 emu/g with the enhanced coercivity (HC) from 335 Oe to 1700 Oe with the substitution of Ni2+ ions is in corroboration with electron paramagnetic resonance (EPR) measurements. The enhanced EPR resonance field (Hres = 2335 Oe - 3261 Oe) with the substitution of Ni2+ ions is attributed to the generation of oxygen vacancies and defects, which are predominant in Ni0.8Co0.2Fe2O4, resulting in significantly enhanced electrochemical performance. Therefore, the three-electrode system was utilized to investigate the electrochemical properties of NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs. The Ni-substituted CoFe2O4 MNPs have demonstrated significantly enhanced capacity retention of 77 % even after 5000 cycles in 1 M H2SO4 electrolyte solution. NixCo1-xFe2O4 (0 ≤ x ≤ 0.8) MNPs exhibit an excellent specific capacity (Cs) of 794.5 F/g at a current density of 1 A/g, signifies the rate of redox reaction at surface electrolyte interface (SEI) is greatly influenced by the surface to volume ratio. Thus, with the enhancement of Ni2+ ions, redox reaction kinetics might become more efficient resulting in the enhanced charge storage capacity.

Preliminary ESR dating results of fault barite shed new insights into the retrospective history of bedrock fault activities in basaltic regions

The chronology of fault activity in bedrock is critical to constraining and understanding periods of active faulting, assessing seismic hazards, and mitigating the effects of earthquakes. However, because of the lack of suitable materials for dating, the temporal reconstruction of faulting in bedrock remains highly challenging for geologists. In the present study, we determine for the first time the electron spin resonance (ESR) ages of fault barite (BaSO4), which is produced by episodes of intense faulting on basalt bedrock fault surfaces. Three barite samples were obtained from a basalt fault section (27°5′23″N, 100°25′45″E, 1.8 km above sea level) of the Lijiang–Xiaojinhe Fault (LXF), southeastern Tibetan Plateau, for ESR measurements. Similar to marine barite, the ESR spectrum of fault barite shows an electron-type center with g = 2.0037, 2.0034, and 2.0028 attributed to SO3−. The signal intensity systematically increased with increasing gamma-ray dose. Dose rates were calculated using a model based on the location and burial depth of the barite samples, as well as their surrounding bedrock. The three barite samples yield ESR ages of 131 ± 26, 503 ± 61, and 1416 ± 246 ka, respectively, which indicate that the LXF was active during the Early and Middle Pleistocene. The three ESR ages for fault barite from basalt extend the time range of activity of the LXF compared with previous carbonate ESR and radiocarbon dating results. Consequently, we propose that ESR dating of barite is valuable for reconstructing the history of bedrock fault activity. However, given that this investigation represents a preliminary application of the fault-barite ESR method, further study is needed to confirm its usefulness and the accuracy and precision of dating results.

Ionic Covalent-Organic Frameworks Composed of Anthryl-Extended Viologen as a Kind of Electrochemiluminescence Luminophore.

Nowadays, covalent-organic frameworks (COFs) integrated with the electrochemiluminescence (ECL) behavior are highly desired owing to the significant advantages including multifunctionality, high sensitivity, and low background noise. Here, two ionic COFs (iCOFs) consisting of the anthryl-extended viologen as the backbone were designed and synthesized via the Zincke reaction. It is found for the first time that the as-prepared iCOFs accompanied by potassium persulfate as the coreactant can provide a clear ECL response in a water-bearing medium. The maximum ECL emissions of the iCOFs were in agreement with the photoluminescence spectra. Besides, cyclic voltammetry and electron paramagnetic resonance measurements reveal that the pyridinium unit was electrochemically reduced to afford the free radical. Then, it reacted with SO4·- to generate the excited-state [iCOF]*. Finally, [iCOF]* quickly returned to its ground state coupled with a clear ECL emission, yielding a maximum ECL quantum efficiency of 23.4% compared with tris(2,2'-bipyridyl) ruthenium(II) as the benchmark. In brief, the current study opens a way to develop a kind of ECL emitter that holds great potential in sensing, imaging, and light-emitting devices.

Compact Electron Paramagnetic Resonance on a Chip Spectrometer Using a Single Sided Permanent Magnet.

Electron paramagnetic resonance (EPR) spectroscopy provides information about the physical and chemical properties of materials by detecting paramagnetic states. Conventional EPR measurements are performed in high Q resonator using large electromagnets which limits the available space for operando experiments. Here we present a solution toward a portable EPR sensor based on the combination of the EPR-on-a-Chip (EPRoC) and a single-sided permanent magnet. This device can be placed directly into the sample environment (i.e., catalytic reaction vessels, ultrahigh vacuum deposition chambers, aqueous environments, etc.) to conduct in situ and operando measurements. The EPRoC reported herein is comprised of an array of 14 voltage-controlled oscillator (VCO) coils oscillating at 7 GHz. By using a single grain of crystalline BDPA, EPR measurements at different positions of the magnet with respect to the VCO array were performed. It was possible to create a 2D spatial map of a 1.5 mm × 5 mm region of the magnetic field with 50 μm resolution. This allowed for the determination of the magnetic field intensity and homogeneity, which are found to be 254.69 mT and 700 ppm, respectively. The magnetic field was mapped also along the vertical direction using a thin film a-Si layer. The EPRoC and permanent magnet were combined to form a miniaturized EPR spectrometer to perform experiments on tempol (4-hydroxy-2,2,6,6-teramethylpiperidin-1-oxyl) dissolved in an 80% glycerol and 20% water solution. It was possible to determine the molecular tumbling correlation time and to establish a calibration procedure to quantify the number of spins within the sample.

Light-Induced Metallic and Paramagnetic Defects in Halide Perovskites from Magnetic Resonance.

Halide perovskites are promising next-generation solar cell materials, but their commercialization is hampered by their propensity to degrade under operating conditions, particularly under heat, humidity, and light. Identifying degradation products and linking them to the degradation mechanism at the atomic scale is necessary to design more stable perovskite materials. Here we use magnetic resonance methods to identify and characterize the formation of both metallic lead clusters and Pb3+ defects upon light-induced degradation of methylammonium lead halide perovskite using nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) measurements. Paramagnetic relaxation enhancement (PRE) of the 1H NMR resonances demonstrates the presence of localized paramagnetic Pb3+ defects, a large Knight shift of the 207Pb NMR proves the presence of lead metal, and their relative proportions are determined by the differing temperature dependence in variable-temperature EPR. This work reconciles previous conflicting literature results, enabling the use of EPR spectroscopy to monitor photodegradation of perovskite devices.