Effect of true triaxial principal stress unloading rate on strain energy density of sandstone.

Deep rock are often in a true triaxial stress state. Studying the impacts of varying unloading speeds on their strain energy (SE) density is highly significant for predicting rock stability. Through true triaxial unloading principal stress experiments and true triaxial stress equilibrium unloading experiments on sandstone, this paper proposes a method to compute the SE density in a true triaxial compressive unloading principal stress test. This method aims to analyze the SE variation in rocks under the action of true triaxial unloading principal stresses. Acoustic emission is used to verify the correctness of the SE density calculation method in this paper. This study found that: (1) Unloading in one principal stress direction causes the SE density to rise in the other principal stress directions. This rise in SE, depending on its reversibility, can be categorized into elastic and dissipated SE. (2)When unloading principal stresses, the released elastic SE density in the unloading direction is influence by the stress path and rate. (3) The higher the unloading speed will leads to greater increases in the input SE density, elastic SE density, and dissipative SE density in the other principal stress directions. (4) The dissipated SE generated under true triaxial compression by unloading the principal stress is positively correlated with the damage to the rock; with an increase in unloading rate, there is a corresponding increase in the formation of cracks after unloading. (5) Utilizing the stress balance unloading test, we propose a calculation method for SE density in true triaxial unloading principal stress tests.

Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen Evolution Reaction.

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to ß-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals ß-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate ß-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared ß-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.

Hydrogel Nanoparticles Enable Nucleation Barrier Regulation and Ion Anchoring as an Alternative Pathway for Monosodium Urate Monohydrate Crystallization Control.

Gout flare-up, commonly resulting from monosodium urate monohydrate (MSUM) crystallization, has led to painful inflammatory arthritis among hundreds of millions of people. Herein, a kind of hydrogel nanoparticles (HNPs) with specific properties was developed, aimed at providing a promising pathway for MSUM crystallization control. The experimental and molecular dynamics simulation results synchronously indicate that the fabricated HNPs achieve efficient inhibition of MSUM crystallization governed by the mechanism of "host-guest interaction" even under very low-dose administration. HNPs as the host dispersed in the hyperuricemic model effectively lift the relative heterogeneous nucleation barrier of the MSUM crystal and hinder solute aggregation with strong electronegativity and hydrophobicity. The initial appearance of MSUM crystals was then delayed from 94 to 334 h. HNPs as the guest on the surface of the formed crystal can decelerate the growth rate by anchoring ions and occupying the active sites on the surface, and the terminal yield of the MSUM crystal declined to less than 1% of the control group. The good biocompatibility of HNPs (cell viability > 94%) renders it possible for future clinical applications. This study can guide the rational design of inhibitory nanomaterials and the development of their application in the control of relevant pathological crystallization.

Ecological risk assessment of heavy metal(loid)s in riverine sediments along the East China Sea: A large-scale integrated analysis.

This study comprehensively assesses spatial distribution, pollution levels, and potential sources of heavy metal(loid)s in surface sediments across multiple river systems along the coastal area of the East China Sea. Copper in Qiantang River and Xiangshan Bay showed higher concentations and exceeded the threshold effect value, while the higher content of Lead was mainly found in the Saijiang River, Oujiang River, and Minjiang River. Heavy metal(loid)s in the alluvium of Qiantang River, Jiaojiang River, and Yangtze River showed low to moderate pollution levels, with Cd posing the highest ecological risk, followed by Hg. Meanwhile, Qiantang River, Jiaojiang River, Yangtze River, and Oujiang River exhibited considerable to moderate ecological risks and low toxic risk. PMF model analysis results reveal that concentrations of Cr, Ni, and As were closely related with natural geogenic input (36.56 %), while industrial and traffic activities (48.77 %) were primary source of Cu, Pb, Zn, and Hg, and main source of Cd was agricultural emissions (14.67 %).

Harnessing sub-comb dynamics in a graphene-sensitized microresonator for gas detection.

Since their inception, frequency combs generated in microresonators, known as microcombs, have sparked significant scientific interests. Among the various applications leveraging microcombs, soliton microcombs are often preferred due to their inherent mode-locking capability. However, this choice introduces additional system complexity because an initialization process is required. Meanwhile, despite the theoretical understanding of the dynamics of other comb states, their practical potential, particularly in applications like sensing where simplicity is valued, remains largely untapped. Here, we demonstrate controllable generation of sub-combs that bypasses the need for accessing bistable regime. And in a graphene-sensitized microresonator, the sub-comb heterodynes produce stable, accurate microwave signals for high-precision gas detection. By exploring the formation dynamics of sub-combs, we achieved 2 MHz harmonic comb-to-comb beat notes with a signal-to-noise ratio (SNR) greater than 50 dB and phase noise as low as - 82 dBc/Hz at 1 MHz offset. The graphene sensitization on the intracavity probes results in exceptional frequency responsiveness to the adsorption of gas molecules on the graphene of microcavity surface, enabling detect limits down to the parts per billion (ppb) level. This synergy between graphene and sub-comb formation dynamics in a microcavity structure showcases the feasibility of utilizing microcombs in an incoherent state prior to soliton locking. It may mark a significant step toward the development of easy-to-operate, systemically simple, compact, and high-performance photonic sensors.

The comparison between fixed versus degressive doses of medroxyprogesterone acetate combined with letrozole in patients of progestin-primed ovarian stimulation protocol: a propensity score-matched study.

Objective: To explore the cycle characteristics and pregnancy outcomes of progestin-primed ovarian stimulation (PPOS) using fixed versus degressive doses of medroxyprogesterone acetate (MPA) in conjunction with letrozole (LE) in infertile women by propensity score matching (PSM) analysis. Design: A retrospective cohort study. Setting: Tertiary-care academic medical center. Population: A total of 3173 infertile women undergoing their first in vitro fertilization/intracytoplasmic sperm injection (IVF/ICSI) treatment within the period from January 2017 to December 2020. Methods: A total of 1068 and 783 patients who underwent a fixed dose of MPA combined with LE and a degressive dose of MPA combined with LE protocols, respectively, were enrolled in this study. The freeze-all approach and later frozen-thawed embryo transfer (FET) were performed in both groups. Propensity score matching (1:1) was performed. Main outcome measures: The primary outcomes were the dosage of MPA and the incidence of premature luteinizing hormone (LH) surges. The secondary outcomes were the number of oocytes retrieved, the cumulative live birth rate (CLBR) and the fetal malformation rate. Results: We created a perfect match of 478 patients in each group. The dosage of MPA, the LH serum level on the eighth day of stimulation, progesterone (P) level and LH level on the hCG trigger day were significantly higher in the LE + fixed MPA group than in the LE + degressive MPA group (52.1 ± 13.1 mg vs. 44.9 ± 12.5 mg; 5.0 ± 2.7 IU/L vs. 3.7 ± 1.7 IU/L; 0.9 ± 0.5 ng/ml vs. 0.8 ± 0.5 ng/ml; 3.3 ± 2.4 IU/L vs. 2.8 ± 1.9 IU/L; P < 0.01). The duration of Gn, the number of follicles with diameter more than 16 mm on trigger day, the estradiol (E2) level on the hCG trigger day were lower in the LE + fixed MPA group than in the LE + degressive MPA group (9.7 ± 1.7 days vs. 10.3 ± 1.5 days; 5.6 ± 3.0 vs. 6.3 ± 3.0; 1752.5 ± 1120.8 pg/ml vs. 1997.2 ± 1108.5 pg/ml; P < 0.001). No significant difference was found in the incidence of premature LH surge, the number of oocytes retrieved, the number of top-quality embryos, clinical pregnancy rate (CPR), CLBR or fetal malformation rate between the two groups. Conclusion: The combination of a degressive MPA dose with LE proved effective in reducing the total MPA dosage with comparable premature LH surge and pregnancy outcomes in women undergoing the PPOS protocol.

Comprehensive Functional Analysis of the bZIP Family in Bletilla striata Reveals That BsbZIP13 Could Respond to Multiple Abiotic Stresses.

Basic leucine zipper (bZIP) transcription factors (TFs) are one of the largest families involved in plant physiological processes such as biotic and abiotic responses, growth, and development, etc. In this study, 66 members of the bZIP family were identified in Bletilla striata, which were divided into 10 groups based on their phylogenetic relationships with AtbZIPs. A structural analysis of BsbZIPs revealed significant intron-exon differences among BsbZIPs. A total of 63 bZIP genes were distributed across 16 chromosomes in B. striata. The tissue-specific and germination stage expression patterns of BsbZIPs were based on RNA-seq. Stress-responsive expression analysis revealed that partial BsbZIPs were highly expressed under low temperatures, wounding, oxidative stress, and GA treatments. Furthermore, subcellular localization studies indicated that BsbZIP13 was localized in the nucleus. Yeast two-hybrid (Y2H) and bimolecular fluorescence complementation (BiFC) assays suggested that BsbZIP13 could interact with multiple BsSnRK2s. The results of this study provide insightful data regarding bZIP TF as one of the stress response regulators in B. striata, while providing a theoretical basis for transgenic and functional studies of the bZIP gene family in B. striata.

[Distribution, Sources, and Risk Assessment of Microplastics in Surface Sediments of Yellow River Delta Wetland].

Estuarine habitats are a critical zone of the Earth with strong land-sea interactions, that are strongly influenced by human activities. Microplastics (MPs) pollution in the Yellow River Delta (YRD) wetland, a typical young warm-temperate estuarine wetland, has not been comprehensively studied. The morphology, abundance, particle size, and polymer composition of MPs in the surface sediments of the YRD wetland were determined, and the pollution status and ecological risk in the study area were evaluated using the pollution load index (PLI) and potential pollution risk index (PRI). The results showed that the abundance of MPs in the YRD wetland was 20-520 n·kg-1, with a median value of 150 n·kg-1. The MPs were primarily fibers in shape and black in color, with particle size over 1 mm. The polymer components were primarily rayon, polyethylene, polyester, and polyethylene terephthalate. The PLI and PRI values of the MPs in the area were between 0.04-0.96 and 0.00-171.60, respectively, indicating that the pollution of MPs in the YRD wetland was at a slightly polluted level with low ecological risk.

Spatial distribution and sources of heavy metals in the sediment and soils of the Yancheng coastal ecosystem and associated ecological risks.

Studies of heavy metal pollution are essential for the protection of coastal environments. In this study, positive matrix factorization (PMF) and a GeoDetector model were used to evaluate the sources of heavy metal contamination and associated ecological risks along the Yancheng Coastal Wetland. The distribution of heavy metals was shown to be greatly affected by clay content, except for Cr in shoal. Components from 6.5 to 9φ have the strongest ability to absorb heavy metals, where the effects of Cd and Zn sequestration in the wetlands were most apparent. The abilities of various wetland environments to sequester heavy metals were shown to be Spartina alterniflora wetland > woodland > Phragmites australis wetland > aquaculture pond > shoal > paddy > meadow > dry land. The sources of the heavy metals included parent soil material (59%), agriculture (15%), and industrial pollutants (26%). According to the single-factor pollution index, there was no evidence of pollution except Cr and Pb. In general, the heavy metal pollution was insignificant. The order of pollution loading index was shoal > paddy field > dry land > Spartina Alterniflora wetland > aquaculture ponds > woodland > meadow > Phragmites australis wetland. The ecological harm of heavy metal exposure was slight except for Cd and Hg, where vehicle emissions appeared to be the main cause of heavy metal pollution.

Hydrochemical evolution processes of multiple-water quality interfaces (fresh/saline water, saline water/brine) on muddy coast under pumping conditions.

A thorough understanding of the evolution of coastal brine-bearing groundwater systems under the influence of human activities contributes to the sustainable use of coastal groundwater resources. Therefore, this study comprehensively investigated the processes associated with hydrochemical changes in groundwater during brine exploitation based on long-term monitoring data. The dataset comprised 102 samples (including groundwater, seawater, rain and river samples) collected from 1966 to 2021 to capture the hydrochemical variability. Significant changes in the brine water table and concentration between the pre-overexploitation period (1965-2000) and the exploitation period (2000-2021) are observed. From the relationship between stable isotope (δ18O and δ2H) values and Cl- contents, shallow saline water (SSW) near the drawdown cone (with δ18O and δ2H values of -4.66 ‰ ~ -3.57 ‰ and - 42.1 ‰ ~ -32.8 ‰, respectively) is similar geochemically to the brine inside the drawdown cone (with values of -4.30 ‰ ~ -3.10 ‰ and - 39.0 ‰ ~ -32.3 ‰, respectively), indicating that the SSW has a recharge effect on the underground brine. The delta values of major cations were calculated to analyze the hydrochemical processes at different water quality interfaces (saline/freshwater interface, salinewater/brine interface). The results demonstrated that the SSW and deep saline water (DSW) at the offshore brine/saline water interface undergo seawater intrusion, where SSW undergoes a salinization process with cation exchange (Na+ is exchanged for Ca2+ and Mg2+ in clay), while DSW undergoes a freshening process. The SSW at the saline/freshwater interface is affected by freshwater pumping, and the DSW undergoes a salinization process influenced by brine intrusion presenting the common salinization process with cation exchange. The hydrochemical model shows that the brine concentration recovered during the restricted exploitation stage due to the dissolution of gypsum and halite. If no measures are taken to restrict exploitation, then brine will eventually be replaced by saline water.

Geochemical characteristics of heavy metals in surface sediments of the Bohai Strait, China.

The heavy metal (Cr, Cu, Ni, Pb, and Zn) content and particle size of surface sediment samples taken from 123 sites in the Bohai Strait of China were analyzed. All five heavy metals showed a similar distribution in the Bohai Strait, with lower concentrations in the middle and higher concentrations at the sides of the strait. The amount of heavy metals was lowest in the Laotieshan Channel due to the rapid current in this channel. According to our calculated values of the pollution index (Pi), only 1.6 % of the sample sites were polluted by Cr and Cu. The calculated geo-accumulation index (Igeo) values showed that few of the sites were polluted by heavy metals. The level of Pb was controlled by both terrigenous inputs and clay adsorption, while the levels of the other heavy metals (Cr, Cu, Ni, and Zn) were mainly controlled by terrigenous inputs.

Comparison of weight loss and adverse events of obesity drugs in children and adolescents: a systematic review and meta-analysis.

BACKGROUND: The global incidence of childhood obesity is increasing. Currently, there are only few established drugs for treating adolescent obesity. Randomized clinical trials (RCTs) comparing pharmacological interventions in children with obesity are scarce; therefore, we aimed to analyze the relative efficacy and adverse reactions of these drugs and compare the effects of each drug on body mass index (BMI). RESEARCH DESIGN AND METHODS: This meta-analysis focused on the slimming effect, safety, and correlation of metformin, orlistat, exenatide, liraglutide, and topiramate in children with obesity. Several international databases were searched and clinical trials on the treatment of obesity in children in which the drug was administered for ≥ 6 months were included. Changes in BMI before and after treatment were analyzed using a Bayes framework, and the surface under the cumulative ranking was calculated. RESULTS: Of 2102 relevant articles retrieved, 21 RCTs were included in the study. Compared to other drugs, liraglutide reduced BMI the most in children with obesity. However, it was most associated with drug withdrawal due to adverse events while topiramate was least. CONCLUSIONS: Liraglutide had a higher probability of achieving clinically significant weight loss compared with other drugs while topiramate was superior in safety.

UVR Promotes Keratinocyte Phagocytosis and Skin Pigmentation Through TRPA1 Channels.

Purpose: Ultraviolet radiation (UVR) enhances skin pigmentation, which involves the production of melanin by melanocytes and subsequent transfer to keratinocytes. In the epidermis, keratinocyte phagocytosis plays a pivotal role in the process of melanosome transfer to protect DNA of epidermal cells against damage from UVR. Previous research suggested that transient receptor potential channels ankyrin 1 (TRPA1) was required for UVR-induced early melanin synthesis in melanocytes. Currently, there is no evidence that supports the detailed mechanism of TRPA1 for UVR-induced phagocytosis by keratinocytes. Here, we investigated the effect and the possible mechanisms of TRPA1 on keratinocyte phagocytosis and skin pigmentation after UVR exposure. Methods: Flow cytometry was applied to investigate the effect of TRPA1 on intracellular calcium concentration ([Ca2+]ic) and fluorescent microspheres uptake was carried out to analyze phagocytosis in HaCaT cells (human immortalized keratinocytes). Western blotting was applied to measure the protein expression of calcium/calmodulin-dependent protein kinase II (CaMKII), phosphorylated CaMKII and ß-catenin after UVA/UVB exposure. Masson-Fontana staining was applied to observe the effect of XAV-939 (decreasing the expression of ß-catenin) on UVB-induced skin pigmentation in guinea pigs. Results: TRPA1 channels activated by UVR increased the [ca2+]ic and phosphorylation of CaMKII in HaCaT cells. The UVR-induced phagocytosis was regulated by TRPA1 in HaCaT cells. TRPA1 promoted the protein expression of ß-catenin after UVR exposure in HaCaT cells. XAV-939, inhibiting ß-catenin expression, decreased the UVB-induced skin pigmentation on in vivo guinea pig models. Conclusion: Taken together, TRPA1 activated by UVR led to the increase of intracellular calcium, which promoted the phosphorylation of CaMKII, enhancing keratinocyte phagocytosis. Moreover, TRPA1 regulated the protein expression of ß-catenin to exert a lightening effect on skin pigmentation. Our findings suggest that TRPA1 may be a potential therapeutic target for UVR-induced skin pigmentary diseases.

TRPA1 promotes melanosome phagocytosis in keratinocytes via PAR-2/CYLD axis.

BACKGROUND: Keratinocytes are recipients of melanosomes. Although the chemical basis of melanogenesis is well documented, the molecular mechanism of melanosome transfer must be elucidated. TRPA1 is a member of the transient receptor potential A subfamily. Previous studies have shown that inhibition of TRPA1 activity reduces melanin synthesis in human epidermal melanocytes; however, the mechanism remains unknown. OBJECTIVE: This study aimed to investigate the roles and mechanism(s) of action of TRPA1 in keratinocytes. METHODS: The correlation between TRPA1 expression levels and the ability of keratinocytes to phagocytize melanosomes was examined using melanin silver staining. TRPA1 depleted human epidermal keratinocytes and keratinocyte cell lines HaCaT were established using adenovirus-expressing shRNAs against TRPA1. The effects of TRPA1 on keratinocytes and HaCaT cells were determined using cell-based analyses, including light stimulation, calcium imaging, melanin phagocytosis, immunoblotting, and co-immunoprecipitation assays. The degree of epidermal pigmentation was determined in a guinea pig model. RESULTS: TRPA1 mediated the phagocytic activity of keratinocytes. TRPA1 knockdown markedly suppressed melanosome transport to keratinocytes. Mechanistically, TRPA1 was required for PAR-2-induced melanosome phagocytosis in keratinocytes. Furthermore, TRPA1 activation indirectly stabilized microtubules by promoting the competitive binding of CYLD and acetylated α-tubulin. In addition, bortezomib (PS-341), a proteasome inhibitor, increased TRPA1 and CYLD expression and promoted phagocytic activity both in vitro and in vivo. CONCLUSIONS: Our findings firstly suggest that TRPA1 promotes melanosome transport in keratinocytes and reveal that TRPA1 is a regulator of PAR-2 activation and microtubule stability via the PAR-2/CYLD axis.

Sensitive and Enzyme-Free Pathogenic Bacteria Detection Through Self-Circulation of Molecular Beacon.

This research exhibits the design of a feasible, enzyme-free and sensitive fluorescent sensing assay for the detection of Staphylococcus aureus (S. aureus), using self-circulation of molecular beacons. With protein A on S. aureus as identifying target, the capture probe binds on the surface of S. aureus based on interaction between its aptamer section and protein A. Recognition of protein A by aptamer section in capture probe leads to allosterism of capture probe, exposing initiator section to activate the following self-circulation. After multiple circulation-based signal amplification, the method exhibits a favorable detection sensitivity and shows a promising prospect for the keratitis-related pathogenic bacteria detection. The highlights of the sensing assay are as follows: (i) capture probe is designed with aptamer section which endows the method a high selectivity; (ii) signal of bacteria is converted to nucleic acid signal after recognition of target bacteria by capture probe; and (iii) high sensitivity of method is derived from the self-circulation process. Therefore, we believe that the strategy can provide a useful platform for target bacteria detection and thus contribute to the diagnosis of infectious diseases.

Expression of CDK13 Was Associated with Prognosis and Expression of HIF-1α and beclin1 in Breast Cancer Patients.

OBJECTIVE: To investigate role and clinical significance of CDK13 in breast cancer patients. METHODS: A total of 189 cases of breast cancer were enrolled during March 2013 to March 2015. Immunohistochemistry (IHC) was used for measurement of CDK13, HIF-1α and beclin1. Clinical characteristics of age, BMI, TNM stage, pathological types, and tumor diameter, were recorded. Patients' 5-year overall survival and recurrence were followed up. All patients were followed up for 5 years or to the last follow-up. RESULTS: The expression levels of CDK13 and HIF-1αin breast cancer tissues were up-regulated and beclin1 was down-regulated than in the paracancerous non-tumor tissues. CDK13 was positively correlated with HIF-1α and negatively correlated with beclin1 in breast cancer tissues. The patients with higher expression of CDK13 showed significantly higher rates of TNM III-IV, higher rates of lymph node metastasis, distant metastasis and larger tumor size. The mortality and recurrence rates were higher in high expression CDK13 patients than in low CDK13 expression patients, however with no significant difference. K-M curve showed patients with higher CDK13 showed lower 5-year overall survival and lower disease-free survival time, however with no significant difference. CONCLUSION: CDK13 was overexpressed in breast cancer tissues, and patients with higher CDK13 had poorer clinical outcomes. Further studies are still needed to reveal the clinical significance of CDK13 in breast cancer.

Performance of MoS2/Zr Composite Coatings at Different Deposition Temperatures.

The properties of the MoS2/Zr coatings can be significantly affected by the deposition temperature. In this study, the MoS2/Zr composite coatings were fabricated on the cemented carbide surface, utilizing the duplex deposition technology at various deposition temperatures. The effects of deposition temperature on the mechanical and friction properties of the MoS2/Zr coatings were systematically studied. Results exhibited that as the deposition temperature increased, the adhesion force increased first and then decreased, and the coating thickness and micro-hardness gradually increased. Dry sliding tests against a hardened steel ring showed that the tribological behaviors and wear mechanisms of the MoS2/Zr coatings varied with deposition temperature, which were due to the changing mechanical properties of coatings caused by the temperature. The coatings deposited at a temperature of 180 °C and 200 °C possessed preferable comprehensive mechanical and tribological properties.

Graded bulk-heterojunction enables 17% binary organic solar cells via nonhalogenated open air coating.

Graded bulk-heterojunction (G-BHJ) with well-defined vertical phase separation has potential to surpass classical BHJ in organic solar cells (OSCs). In this work, an effective G-BHJ strategy via nonhalogenated solvent sequential deposition is demonstrated using nonfullerene acceptor (NFA) OSCs. Spin-coated G-BHJ OSCs deliver an outstanding 17.48% power conversion efficiency (PCE). Depth-profiling X-ray photoelectron spectroscopy (DP-XPS) and angle-dependent grazing incidence X-ray diffraction (GI-XRD) techniques enable the visualization of polymer/NFA composition and crystallinity gradient distributions, which benefit charge transport, and enable outstanding thick OSC PCEs (16.25% for 300 nm, 14.37% for 500 nm), which are among the highest reported. Moreover, the nonhalogenated solvent enabled G-BHJ OSC via open-air blade coating and achieved a record 16.77% PCE. The blade-coated G-BHJ has drastically different D-A crystallization kinetics, which suppresses the excessive aggregation induced unfavorable phase separation in BHJ. All these make G-BHJ a feasible and promising strategy towards highly efficient, eco- and manufacture friendly OSCs.

Direct Observation of Oxygen Evolution and Surface Restructuring on Mn2O3 Nanocatalysts Using In Situ and Ex Situ Transmission Electron Microscopy.

Direct observation of oxygen evolution reaction (OER) on catalyst surface may significantly advance the mechanistic understanding of OER catalysis. Here, we report the first real-time nanoscale observation of chemical OER on Mn2O3 nanocatalyst surface using an in situ liquid holder in a transmission electron microscope (TEM). The oxygen evolution process can be directly visualized from the development of oxygen nanobubbles around nanocatalysts. The high spatial and temporal resolution further enables us to unravel the real-time formation of a surface layer on Mn2O3, whose thickness oscillation reflects a partially reversible surface restructuring relevant to OER catalysis. Ex situ atomic-resolution TEM on the residual surface layer after OER reveals its amorphous nature with reduced Mn valence and oxygen coordination. Besides shedding light on the dynamic OER catalysis, our results also demonstrate a powerful strategy combining in situ and ex situ TEM for investigating various chemical reaction mechanisms in liquid.

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co3O4.

Nanostructured transition-metal oxides have been under intensive investigation for their tantalizing potential as anodes of next-generation lithium-ion batteries (LIBs). However, the exact mechanism for nanostructures to influence the LIB performance remains largely elusive. In this work, we discover the nanostructure-mediated lithiation mechanism in Co3O4 anodes using ex situ transmission electron microscopy (TEM) and X-ray diffractometry: while Co3O4 nanosheets exhibit a typical two-step conversion reaction (from Co3O4 to CoO and then to Co0), Co3O4 nanoarrays can go through a direct conversion from Co3O4 to Co0 at a high discharge rate. Such nanostructure-dependent lithiation can be rationalized by the slow lithiation kinetics intrinsic to Co3O4 nanoarrays, which at a high discharge rate may cause local accumulation of lithium to initiate a one-step Co3O4-to-Co0 conversion. Combined with the larger volume change observed in Co3O4 nanoarrays, the slow lithiation kinetics can lead to inhomogeneous expansion with large stress developed at the reaction front, which can eventually cause structure failure and irreversible capacity loss, as explicitly observed by in situ TEM as well as galvanostatic discharge-charge measurement. Our observation resolves the nanostructure-dependent lithiation mechanism of Co3O4 and provides important insights into the interplay among lithiation kinetics, phase evolution, and lithium-storage performance, which can be translated into electrode design strategies for next-generation LIBs.