Post-device Dimethylamine Treatment Enables Stable and Efficient Perovskite Solar Cells.

The incorporation of organic ligands via post-device treatment is an effective strategy to improve the stability of perovskite solar cells (PSCs). Although the active area is protected by metal electrode under post-treatment, the aggression of post-treatment ligands into active area cannot be avoided thoroughly. Unfortunately, the size of long-chain amines is too large, and the three-dimensional (3D) perovskite cannot maintain its 3D perovskite structure once the cation substitution occurs during the post-treatment. Despite that the low-dimensional (LD) perovskites are beneficial to stability, long-chain amines are harmful to carrier transport in PSCs. Here, we introduce dimethylamine (DMA), a slightly oversized cation that can be doped into 3D perovskite structure, for post-device treatment to improve the efficiency and stability of PSCs. After exposure to DMA gas, the inactive area of Cs/FA/MA mixed cation perovskite device that is not covered by metal electrode is converted into LD perovskite, passivating the defects of 3D perovskite in the active region, suppressing non-radiation recombination and ion migration. As a result, we achieved a power conversion efficiency (PCE) of 22.29 % with negligible hysteresis and better stability after DMA post-treatment, which is much higher than that (20.40 %) of the control device.

Response rate and safety of antidepressants combined with electroconvulsive therapy in adolescent depression: Real-world clinical application.

BACKGROUND: METHODS: This study included 210 depression patients receiving antidepressants and ECT. The symptoms of depression were examined with the Hamilton Depression Scale (HAMD) and Clinical Global Impressions Scale (CGI) at baseline and the end of treatment. Response and safety were compared among adolescent and adult patients. RESULTS: For adolescents, the response rate (much improved or very much improved) was 80.9 %, and CGI-Severity (CGI-S), HAMD, and suicide factor scores were significantly changed as compared to baseline (P < 0.001), results of which were similar to the adult group. There were no significant differences in HAMD, CGI scores between adolescent and adult depression before or after treatment (P > 0.05). Notably, adolescents expressed stronger suicidal intent than adults, and ECT observably relieved it. Side effects (memory problems, headache, nausea/vomiting, muscle soreness) in adolescents were not statistically different from those in adults (P > 0.05). LIMITATIONS: As data were derived from a single center, the generalizability of results may be limited, and the potential factors affecting the efficacy of ECT were not further explored. CONCLUSION: Antidepressants combined with ECT are associated with high response rate and safety for treating depression, regardless of age. A stronger expression of suicide ideation was observed in depressed adolescents, and side effects of ECT were similar to the adults.

Recent Advances in Manganese-Based Materials for Electrolytic Water Splitting.

Developing earth-abundant and highly effective electrocatalysts for electrocatalytic water splitting is a prerequisite for the upcoming hydrogen energy society. Recently, manganese-based materials have been one of the most promising candidates to replace noble metal catalysts due to their natural abundance, low cost, adjustable electronic properties, and excellent chemical stability. Although some achievements have been made in the past decades, their performance is still far lower than that of Pt. Therefore, further research is needed to improve the performance of manganese-based catalytic materials. In this review, we summarize the research progress on the application of manganese-based materials as catalysts for electrolytic water splitting. We first introduce the mechanism of electrocatalytic water decomposition using a manganese-based electrocatalyst. We then thoroughly discuss the optimization strategy used to enhance the catalytic activity of manganese-based electrocatalysts, including doping and defect engineering, interface engineering, and phase engineering. Finally, we present several future design opportunities for highly efficient manganese-based electrocatalysts.

Graphene Nano-Blister in Graphite for Future Cathode in Dual-Ion Batteries: Fundamentals, Advances, and Prospects.

The intercalating of anions into cost-effective graphite electrode provides a high operating voltage, therefore, the dual-ion batteries (DIBs) as novel energy storage device has attracted much attention recently. The "graphene in graphite" has always existed in the graphite cathode of DIBs, but has rarely been researched. It is foreseeable that the graphene blisters with the intact lattice structure in the shell can utilize its ultra-high elastic stiffness and reversible lattice expansion for increasing the storage capacity of anions in the batteries. This review proposes an expected "blister model" by introducing the high elasticity of graphene blisters and its possible formation mechanism. The unique blisters composed of multilayer graphene that do not fall off on the graphite surface may become indispensable in nanotechnology in the future development of cathode materials for DIBs.

Controllable synthesis of Co-Al layered double hydroxides with different anionic intercalation layers for the efficient removal of methyl orange.

In order to investigate the effect of the types of interlayer anions on the adsorption performance of LDHs, herein, we synthesized three cobalt-aluminum layered double hydroxides (CoAl-LDHs) with different interlayer anions (NO3-/Cl-/CO32-). The experimental results demonstrate that the CoAl-LDH (Cl-) exhibited high adsorption capacity of 1372.1 mg/g at room temperature and the fastest adsorption rate on methyl orange (MO), mainly attributed to the excellent ion exchange capacity and high specific surface area and pore volume. Furthermore, the ion exchange driven by electrostatic interaction, hydrogen bonding, and surface complexation might be the main mechanisms for MO adsorption on CoAl-LDH (Cl-) and CoAl-LDH (NO3-). However, the MO adsorption on CoAl-LDH (CO32-) was strongly pH-dependent and the optimal pH value was about 3.5. Additionally, the supramolecular structure of CoAl-LDHs-MO was formed through electrostatic interaction, hydrogen bonding, and surface complexation between the host hydroxide layers and the guest MO- after adsorption equilibrium. An in-depth understanding of the differences in the adsorption performance of three anion-intercalated CoAl-LDHs will provide opportunities for further improvement of the adsorption capacity and exhibit a bright future for the design and optimization of efficient nano-adsorbents shortly.

Strategy of Enhancing Built-in Field to Promote the Application of C-TiO2 /SnO2 Bilayer Electron Transport Layer in High-Efficiency Perovskite Solar Cells (24.3%).

Combining two kinds of electron transport layer (ETL) which have complementary advantages into a bilayer structure to form a bilayer ETL is an effective way to transcend inherent limitations of single-layer ETL, which is very helpful in the development of perovskite solar cells (PSCs). In this work, a strategy is proposed to break constraints on the application of the staggered bilayer ETL in high-efficiency PSC, namely utilizing a built-in field to overcome the dilemma in ECBM making it possible to improve VOC and FF simultaneously by tuning the Fermi level of ETLs properly. According to the strategy, a bilayer ETL structure comprised of C-TiO2 and SnO2 layer and corresponding Li-doping process are developed, and the characterization results confirm the effectiveness of the strategy, making the potentials of the C-TiO2 (Li)/SnO2 bilayer ETL fully released for its application in high-efficiency PSCs: a VOC of 1.201 V for an ordinary triple-cation-perovskite-based PSC and a photoelectric conversion efficiency of 24.3% for a low-bandgap-perovskite-based PSC with high haze FTO superstrate are successfully achieved, indicating that the C-TiO2 (Li)/SnO2 bilayer ETL is a successful application paradigm of the proposed strategy and very promising in the application of high-efficiency PSCs.

Efficient degradation of sulfamethoxazole under visible light irradiation by polyaniline/copper sulfide composite photocatalyst.

A novel composite photocatalyst polyaniline/copper sulfide (PANI/CuS) was successfully prepared using an in situ precipitation method. The surface morphology, internal structure, thermal stability, electronegativity, and visible light photocatalytic activity of PANI/CuS were analyzed by a series of characterization methods. Sulfamethoxazole (SMX) was used as the representative pollutant; the degradation effect, degradation kinetic, and influencing factor of SMX by PANI/CuS under visible light were systematically investigated. The degradation mechanism of SMX by PANI/CuS was explained by a series of free radical quenching experiments and electron paramagnetic resonance spectroscopy experiments. The following were the main conclusions through the above research. First, the degradation effect of SMX by composite PANI/CuS was better than that by pure CuS under the same experimental conditions, which indirectly proved that the addition of PANI could effectively delay the photochemical corrosion of CuS. Next, when the dosage of PANI/CuS was 0.04 g/L, initial concentration of SMX was 5 ppm, pH was 2.0, and the simulated visible light was 500 W, the degradation effect of SMX was as high as 72.13%. Last, the hole (h+) played a major role and the superoxide radical (·O2-) played an auxiliary role in the degradation process of SMX by PANI/CuS; persistent free radicals exist simultaneously.

ß-Alanine-Anchored SnO2 Inducing Facet Orientation for High-Efficiency Perovskite Solar Cells.

SnO2 films as a promising electron transport layer (ETL) have been widely used in planar-type perovskite solar cells to achieve an impressive improvement in the conversion efficiency. However, compared with a mesoporous ETL, the interfacial charge carrier transfer of the SnO2 ETL is severely limited due to the issues of oxygen vacancy defects and crystal lattice mismatch between SnO2 and the perovskite, which generally leads to the growth of randomly stacked and porous perovskite layers and subsequently impacts the charge transport and transfer properties. In this work, we developed a facile approach by inducing a bifunctional molecule, ß-alanine, into the SnO2 ETL, which can serve as a bridge to modulate the interfacial charge transfer and the perovskite crystallization kinetics. Benefited by the interfacial ß-alanine, we grew a highly orientational perovskite layer that exhibited superior charge transport properties. Meanwhile, the ß-alanine caused an intimate connection between the perovskite and SnO2 to enhance the interfacial charge transfer. As a result, the power conversion efficiency (PCE) of the ß-alanine-modified device achieved a much-improved value of 19.67% and showed high reproducibility. This work provides a way for developing a high-performance ETL toward the scalable fabrication of highly efficient PSCs.

Nomogram for predicting survival of patients with metastatic nonfunctioning pancreatic neuroendocrine tumors: A SEER based study.

ABSTRACT: More attention has been placed on nonfunctioning pancreatic neuroendocrine tumors due to the increase in its incidence in recent years. Whether tumor resection at the primary site of metastatic NFpNET is effective remains controversial. Moreover, clinicians need a more precise prognostic tool to estimate the survival of these patients.Patients with metastatic NFpNET were extracted from the Surveillance, Epidemiology, and End Results (SEER) database. Significant prognostic factors were identified using a multivariate Cox regression model and included in the nomogram. Coarsened exact matching analysis was used to balance the clinical variables between the non-surgical and surgical groups in our study.A total of 1464 patients with metastatic nonfunctioning pancreatic neuroendocrine tumors (NFpNETs) were included in our cohort. Multivariate analysis identified age, sex, tumor size, differentiated grade, lymph node metastases, resection of primary tumors, and marital status as independent predictors of metastatic NFpNET. The nomogram showed excellent accuracy in predicting 1-, 3-, and 5-year overall survival, with a C-index of 0.812. The calibration curve revealed good consistency between the predicted and actual survival.Coarsened exact matching analysis using SEER data indicated the survival advantages of resection of primary tumors. Our study is the first to build a nomogram model for patients with metastatic NFpNETs. This predictive tool can help clinicians identify high-risk patients and more accurately assess patient survival times.

Engineered Sn- and Mg-doped hematite photoanodes for efficient photoelectrochemical water oxidation.

A feasible and cost-effective method was developed to improve the photoelectrochemical performance of the hematite (α-Fe2O3) photoanode. Using a hydrothermal method, tin (Sn) and magnesium (Mg) (co-)doped hematite films were prepared and characterized by X-ray diffraction (XRD), X-ray photon spectroscopy (XPS), and Raman spectroscopy. The average particle size of the α-Fe2O3 film varied from 150 to 300 nm. The photocurrent density of Sn-/Mg-co-doped α-Fe2O3 reached a maximum of 1.1 mA cm-2 at 1.23 VRHE, which increased approximately 3 times compared to that of pristine α-Fe2O3. It also yielded a maximum applied bias photon-to-current efficiency (ABPE) of 0.09% at 1.08 V vs. RHE. The excellent PEC activity could be attributed to Mg co-doping relieving the lattice distortion caused by Sn doping, and improving both the charge injection efficiency and charge separation efficiency without obviously changing the carrier concentration, which was proved by electrochemical impedance spectroscopy. This promising co-doping strategy could also be extended to other candidatephotoelectrodes.

High-yield synthesis of Ce modified Fe-Mn composite oxides benefitting from catalytic destruction of chlorobenzene.

Ce-Fe-Mn catalysts were prepared by an oxalic acid assisted co-precipitation method. The influence of Ce doping and calcination temperature on the catalytic oxidation of chlorobenzene (as a model VOC molecule) was investigated in a fixed bed reactor. The Mn3O4 phase was formed in Ce-Fe-Mn catalysts at low calcination temperatures (<400 °C), which introduced more chemisorbed oxygen, and enhanced the mobility of O atoms, resulting in an improvement of the reduction active of Mn3O4 and Fe2O3. Additionally, CeO2 has strong redox properties, and Ce4+ would oxidize Mn x+ and Fe x+. Therefore, the interaction of Ce, Fe and Mn can improve the content of surface chemisorbed oxygen. As compared with Fe-Mn catalysts, the catalytic conversion of chlorobenzene over Ce(5%)-Fe-Mn-400 was about 99% at 250 °C, owing to high specific surface area, Mn3O4 phase, and Ce doping. However, with the increase in roasting temperature, the performance of the catalysts for the catalytic combustion of chlorobenzene was decreased, which probably accounts for the formation of the Mn2O3 phase in Ce-Fe-Mn-500 catalysts, leading to a decrease in the specific surface area and concentration of chemically adsorbed oxygen. As a result, it can be expected that the Ce-Fe-Mn catalysts are effective and promising catalysts for chlorobenzene destruction.

Zn x Cd1-x S tunable band structure-directing photocatalytic activity and selectivity of visible-light reduction of CO2 into liquid solar fuels.

A series of Zn x Cd1-x S monodispersed nanospheres were successfully synthesized with tunable band structures. As-prepared Zn x Cd1-x S solid solutions show much enhanced photocatalytic efficiency for CO2 photoreduction in aqueous solutions under visible light irradiation, relative to pure CdS analog. Methanol (CH3OH) and acetaldehyde (CH3CHO) are the major products of CO2 photoreduction for the solid solutions with x = 0, 0.2, and 0.5. Interestingly, Zn0.8Cd0.2S photocatalyst with a wide band gap can also additionally generate ethanol (CH3CH2OH) besides CH3OH and CH3CHO. The balance between the band structure-directing redox capacity and light absorption should be considered to influence both product yield and selectivity of CO2 photoreduction. The possible photoreduction mechanism was tentatively proposed.

[Micro-invasive embedding combined with montelukast sodium for children cough variant asthma:a randomized controlled trial].

OBJECTIVE: To observe the effects of micro-invasive embedding combined with montelukast sodium and simple montelukast sodium for children cough variant asthma (CVA). METHODS: A total of 240 patients were randomly assigned into an observation group and a control group, 120 cases in each one. Considering of cases dropping, 101 patients in the observation group and 105 cases in the control group were included. Montelukast sodium chewable tablets were applied before sleep for 3 months in the control group, 5 mg a time, once a day. Based on the treatment as the control group, micro-invasive embedding was used for 3 months in the observation group, twice in the first month and once in the other two months. The acupoints were Feishu (BL 13), Danzhong (CV 17), Dingchuan (EX-B 1), and Zusanli (ST 36). Follow-up was conducted 9 months after treatment in the two groups. The cough score, serum immunoglobulin (IgE, IgG, IgA), platelet activating factor (PAF) were observed before and after treatment. The indices were compared before and after treatment and at follow-up, including pulmonary function indices[peak expiratory flow rate (PEF), forced expiratory volume at the 1st second (FEV1)], and small airway function indices[forced expiratory flow rate with remaining 25% vital capacity (MEF25%), forced expiratory flow rate with remaining 50% vital capacity (MEF50%), forced expiratory flow rate with remaining 75% vital capacity (MEF75%) and mid expiratory flow rate (MEF25%-75%)]. Also, the total effects were evaluated. RESULTS: ①The total effective rate in the observation group was 93.1% (94/101), which was better than 87.6% (92/105) in the control group (P<0.05). The cough disappearance time of the cured children in the observation group was (10.38±2.64) d, and it was shorter than (10.72 ±2.60) d of those in the control group (P<0.05). After treatment, the cough score apparently decreased compared with those before treatment in the two groups (both P<0.05), with better result in the observation group (P<0.05). At follow-up, the recurrence frequency of the observation group was (1.43±1.20), and it was less than (1.91±1.71) in the control group (P<0.05). ②The levels of serum IgA and IgG after treatment in the two groups increased, and those of serum IgE and PAF decreased, compared with those before treatment. There was statistically significance except IgG in the control group before and after treatment (all P<0.05), with better Results in the observation group after treatment (all P<0.05). ③ Compared with those before treatment, all the pulmonary function indices were improved obviously after treatment and at follow-up in the two groups (all P<0.05), without statistically significance between the two groups (both P>0.05). ④ There was no statistically significance before and after treatment on small airway function indices in the two groups (all P>0.05). The indices at follow-up increased compared with those before treatment in the two groups (all P<0.05), with better Results in the observation group (all P<0.05). CONCLUSIONS: Micro-invasive embedding combined with montelukast sodium achieved de-finite effect for children CVA, which can improve the body's immune and microcirculation. The effect is better than that of simple montelukast sodium on improving small airway function, etc.

Fabrication of Lead-Free (CH3 NH3 )3 Bi2 I9 Perovskite Photovoltaics in Ethanol Solvent.

The toxicity of lead present in organohalide perovskites and the hazardous solvent systems used for their synthesis hinder the deployment of perovskite solar cells (PSCs). Herein, an environmentally friendly route toward bismuth-based, lead-free (CH3 NH3 )3 Bi2 I9 perovskites that utilize ethanol as the solvent is described. Using this method, dense and homogeneous microstructures were obtained, compared to the porous, rough microstructures obtained using dimethylformamide. Photovoltaic performances were enhanced, with an open-circuit voltage of 0.84 V measured.

Construction of an all-solid-state artificial Z-scheme system consisting of Bi2WO6/Au/CdS nanostructure for photocatalytic CO2 reduction into renewable hydrocarbon fuel.

An all-solid-state Bi2WO6/Au/CdS Z-scheme system was constructed for the photocatalytic reduction of CO2 into methane in the presence of water vapor. This Z-scheme consists of ultrathin Bi2WO6 nanoplates and CdS nanoparticles as photocatalysts, and a Au nanoparticle as a solid electron mediator offering a high speed charge transfer channel and leading to more efficient spatial separation of electron-hole pairs. The photo-generated electrons from the conduction band (CB) of Bi2WO6 transfer to the Au, and then release to the valence band (VB) of CdS to recombine with the holes of CdS. It allows the electrons remaining in the CB of CdS and holes in the VB of Bi2WO6 to possess strong reduction and oxidation powers, respectively, leading the Bi2WO6/Au/CdS to exhibit high photocatalytic reduction of CO2, relative to bare Bi2WO6, Bi2WO6/Au, and Bi2WO6/CdS. The depressed hole density on CdS also enhances the stability of the CdS against photocorrosion.

Construction of unique two-dimensional MoS2-TiO2 hybrid nanojunctions: MoS2 as a promising cost-effective cocatalyst toward improved photocatalytic reduction of CO2 to methanol.

Two-dimensional MoS2 nanosheets were in situ grown on TiO2 nanosheets to form two-dimensional (2D) hybrid nanojunctions, with which MoS2 nanosheets compactly contact with TiO2 to increase the interfacial area. MoS2 was identified as a promising cost-effective substitute for noble metal cocatalysts such as Pt, Au, and Ag, and shows superior activity and selectivity for reducing CO2 to CH3OH in aqueous solution to these metal cocatalysts under UV-vis light irradiation. The photo-luminescence (PL) spectra and transient time-resolved PL decay measurements reveal that the fast electron transfer from TiO2 to MoS2 can minimize charge recombination losses to improve the conversion efficiency of photoreduction. It reveals that Mo-terminated edges of MoS2 nanosheets possess the metallic character and a high d-electron density, and the Mo cation sites may benefit the stabilization of CHxOy intermediates via electrostatic attraction to enhance the CH3OH formation from the reduction of CO2 in aqueous solution.

Z-Scheme Photocatalytic Systems for Promoting Photocatalytic Performance: Recent Progress and Future Challenges.

Semiconductor photocatalysts have attracted increased attention due to their great potential for solving energy and environmental problems. The formation of Z-scheme photocatalytic systems that mimic natural photosynthesis is a promising strategy to improve photocatalytic activity that is superior to single component photocatalysts. The connection between photosystem I (PS I) and photosystem II (PS II) are crucial for constructing efficient Z-scheme photocatalytic systems using two photocatalysts (PS I and PS II). The present review concisely summarizes and highlights recent state-of-the-art accomplishments of Z-scheme photocatalytic systems with diverse connection modes, including i) with shuttle redox mediators, ii) without electron mediators, and iii) with solid-state electron mediators, which effectively increase visible-light absorption, promote the separation and transportation of photoinduced charge carriers, and thus enhance the photocatalytic efficiency. The challenges and prospects for future development of Z-scheme photocatalytic systems are also presented.

Construction and Nanoscale Detection of Interfacial Charge Transfer of Elegant Z-Scheme WO3/Au/In2S3 Nanowire Arrays.

Elegant Z-scheme WO3/Au/In2S3 nanowire arrays were precisely constructed through a facile step-by-step route. Surface potential change on pristine or In2S3-Au coated WO3 single nanowire under dark and illumination detected through a Kelvin probe force microscopy (KPFM) technique indicates that the vectorial holes transfer of In2S3 → Au → WO3 should occur upon the excitation of both WO3 and In2S3. In such charge transfer processes, the embedded Au nanoparticles in the heterojunction systems act as a charge mediator for electrons in the conduction band of WO3 and holes in the valence band of In2S3. The strong charge carrier separation ability of this structure will finally enhance the oxidation ability of WO3 with high concertation of photogenerated holes and, further, leave the free electrons in the In2S3 with long surviving time. Therefore, the unique Z-scheme WO3/Au/In2S3 heterostructure shows great visible-light activity toward photocatalytic reduction of CO2 in the presence of water vapor into renewable hydrocarbon fuel (methane: CH4).

Construction and Nanoscale Detection of Interfacial Charge Transfer of Elegant Z-Scheme WO3/Au/In2S3 Nanowire Arrays.

Elegant Z-scheme WO3/Au/In2S3 nanowire arrays were precisely constructed through a facile step-by-step route. Surface potential change on pristine or In2S3-Au coated WO3 single nanowire under dark and illumination detected through a Kelvin probe force microscopy (KPFM) technique indicates that the vectorial holes transfer of In2S3 → Au → WO3 should occur upon the excitation of both WO3 and In2S3. In such charge transfer processes, the embedded Au nanoparticles in the heterojunction systems act as a charge mediator for electrons in the conduction band of WO3 and holes in the valence band of In2S3. The strong charge carrier separation ability of this structure will finally enhance the oxidation ability of WO3 with high concertation of photogenerated holes and, further, leave the free electrons in the In2S3 with long surviving time. Therefore, the unique Z-scheme WO3/Au/In2S3 heterostructure shows great visible-light activity toward photocatalytic reduction of CO2 in the presence of water vapor into renewable hydrocarbon fuel (methane: CH4).

Hepatic Lesions Detected after Mastectomy, in Breast Cancer Patients with Hepatitis Background May Need to Undergo Liver Biopsy to Rule Out Second Primary Hepatocellular Carcinoma.

PURPOSE: Liver metastasis is a common phenomenon in breast cancer patients. Hepatic lesions detected in breast cancer patients may be easily misdiagnosed as metastatic sites, rather than being treated as primary foci. This descriptive study aims to investigate the clinicopathological characteristics of second primary hepatocellular carcinoma in breast cancer patients and to infer in which circumstances liver biopsy is needed. METHODS: Eighty-one consecutive breast cancer patients with hepatic lesions admitted to our department were retrospectively studied and analyzed from January 2009 to March 2014 according to Warren and Gates' criteria for second primary cancers. RESULTS: Second primary hepatocellular carcinoma was observed in sixteen of seventy eight patients with breast cancer. There was a significant difference in HBV status between the second HCC group and liver metastases group (P<0.0001). There was no significant difference in age (P = 0.2254) and family history (P = 0.1160) between second primary HCC and metastases group. Two of these patients had synchronous second primary hepatocellular carcinoma and the remaining fourteen patients had metachronous second primary HCC. All sixteen patients were infected with hepatitis, including hepatitis virus B and C, or resolved HBV infection. CONCLUSIONS: Breast cancer patients with either HBV infection or resolved HBV infection, regardless of an elevated AFP level, may receive liver biopsy to avoid unnecessary and inappropriate treatments for metastasis. Awareness of second primary HCC in breast cancer patients needs to be emphasized.