We report the observation of self-doping in perovskite. CH 3 NH 3 PbI 3 was found to be either n-or p-doped by changing the ratio of methylammonium halide (MAI) and lead iodine (PbI 2 ) which are the two precursors for perovskite formation. MAI-rich and PbI 2 -rich perovskite films are p and n self-doped, respectively. Thermal annealing can convert the p-type perovskite to n-type by removing MAI. The carrier concentration varied as much as six orders of magnitude. A clear correlation between doping level and device performance was also observed. V

The direct synthesis of lower (C2 to C4) olefins, key building-block chemicals, from syngas (H2/CO), which can be derived from various nonpetroleum carbon resources, is highly attractive, but the selectivity for lower olefins is low because of the limitation of the Anderson-Schulz-Flory distribution. We report that the coupling of methanol-synthesis and methanol-to-olefins reactions with a bifunctional catalyst can realize the direct conversion of syngas to lower olefins with exceptionally high selectivity. We demonstrate that the choice of two active components and the integration manner of the components are crucial to lower olefin selectivity. The combination of a Zr-Zn binary oxide, which alone shows higher selectivity for methanol and dimethyl ether even at 673 K, and SAPO-34 with decreased acidity offers around 70% selectivity for C2-C4 olefins at about 10% CO conversion. The micro- to nanoscale proximity of the components favors the lower olefin selectivity.

Zn–ZrO2/SSZ-13 catalyzed direct conversion of syngas into lower olefins via methanol/DME intermediates with 77% selectivity at 29% CO conversion.

A bifunctional catalyst composed of ZnGaO with a spinel structure and molecular sieve SAPO-34 catalyses the direct conversion of CO to C-C olefins with a selectivity of 86% and a CO conversion of 13% at 370 °C. The oxygen vacancies on ZnGaO surfaces are responsible for CO activation, forming a methanol intermediate, which is then converted into C-C olefins in SAPO-34.

Transformation of syngas (H2/CO) and hydrogenation of CO2 into lower olefins are attractive routes for chemical utilization of various carbon resources and CO2, but both suffer from limited product selectivity. Tandem catalysis that integrates the activation of CO or CO2 to an intermediate and the subsequent controllable C–C bond formation to form lower olefins offers a promising approach. Here, we report the hydrogenation of both CO and CO2 over bifunctional catalysts composed of a spinel binary metal oxide and SAPO-34. ZnAl2O4/SAPO-34 and ZnGa2O4/SAPO-34 are found to be highly selective for the synthesis of lower olefins from both CO and CO2. Our studies reveal that the oxygen vacancy site on metal oxides plays a pivotal role in the adsorption and activation of CO or CO2, while the −Zn–O– domain accounts for H2 activation. We demonstrate that methanol and dimethyl ether formed on metal oxide are the reaction intermediates, which are subsequently converted to lower olefins by the Brønsted acid sites in zeolite. The hydrogenation of CO and CO2 on metal oxide surfaces proceeds via the same formate and methoxide species. We elucidate that the water–gas shift reaction on oxide surfaces is responsible for CO2 formation during syngas conversion. The cofeeding of CO2 in syngas offers a useful strategy to inhibit CO2 formation.

Interfacial electronic properties of the CH3NH3PbI3 (MAPbI3)/MoOx interface are investigated using ultraviolet photoemission spectroscopy and X-ray photoemission spectroscopy. It is found that the pristine MAPbI3 film coated onto the substrate of poly (3,4-ethylenedioxythiophene) poly(styrenesulfonate)/indium tin oxide by two-step method behaves as an n-type semiconductor, with a band gap of ∼1.7 eV and a valence band edge of 1.40 eV below the Fermi energy (EF). With the MoOx deposition of 64 Å upon MAPbI3, the energy levels of MAPbI3 shift toward higher binding energy by 0.25 eV due to electron transfer from MAPbI3 to MoOx. Its conduction band edge is observed to almost pin to the EF, indicating a significant enhancement of conductivity. Meanwhile, the energy levels of MoOx shift toward lower binding energy by ∼0.30 eV, and an interface dipole of 2.13 eV is observed at the interface of MAPbI3/MoOx. Most importantly, the chemical reaction taking place at this interface results in unfavorable interface energy level alignment for hole extraction. A potential barrier of ∼1.36 eV observed for hole transport will impede the hole extraction from MAPbI3 to MoOx. On the other hand, a potential barrier of ∼0.14 eV for electron extraction is too small to efficiently suppress electrons extracted from MAPbI3 to MoOx. Therefore, such an interface is not an ideal choice for hole extraction in organic photovoltaic devices.

The direct synthesis of lower (C 2 to C 4 )o lefins,k ey building-blockchemicals,from syngas (H 2 /CO), which can be derived from various nonpetroleum carbon resources,ishighly attractive,but the selectivity for lower olefins is lowbecause of the limitation of the Anderson-Schulz-Flory distribution. We report that the coupling of methanol-synthesis and methanolto-olefins reactions with abifunctional catalyst can realizethe direct conversion of syngas to lower olefins with exceptionally high selectivity.W ed emonstrate that the choice of two active components and the integration manner of the components are crucial to lower olefin selectivity.The combination of aZr-Zn binary oxide,w hich alone shows higher selectivity for methanol and dimethyl ether even at 673 K, and SAPO-34 with decreased acidity offers around 70 %s electivity for C 2 -C 4 olefins at about 10 %COconversion. The micro-to nanoscale proximity of the components favors the lower olefin selectivity.

BackgroundConcurrent chemoradiotherapy (CCRT) is effective in the treatment of locally advanced cervical squamous cell carcinoma (SCC). However, whether treatment outcomes of cervical adenocarcinoma are equivalent to SCC after CCRT has been a topic of debate.MethodsMedical records of cervical cancer patients treated with definitive radiotherapy or CCRT in our institute from January 2011 to December 2014 were reviewed. Patients were treated with intensity modulated radiation therapy combined with intracavitary brachytherapy. Weekly cisplatin was the first line regimen of concurrent chemotherapy. The treatment outcomes of patients with SCC and adenocarcinoma were compared with a multivariate Cox regression model, and log-rank method before and after propensity score matching (1:1).ResultsA total of 815 patients with stage IB-IVA cervical cancer were included, with 744 patients in the SCC group and 71 patients in adenocarcinoma group. The median follow-up period was 36.2 months (range, 1.0–76.2 months). The 3-year overall survival (OS), disease-free survival (DFS), pelvic control and distant control rates of patients in the SCC group and adenocarcinoma group were 85.2 and 75.4% (p = 0.005), 77.5 and 57.3% (p < 0.001), 89.0 and 74.0% (p = 0.001) and 86.0 and 74.4% (p = 0.011), respectively. After multivariate analysis, histology was an independent factor of OS (p = 0.003), DFS (p < 0.001), pelvic control (p = 0.002) and distant control (p = 0.003). With propensity score matching, 71 pairs of patients were selected. After matching, the OS (p = 0.017), DFS (p = 0.001), pelvic control (p = 0.015) and distant control (p = 0.009) of patients with adenocarcinoma were poorer than those of patients with SCC. In subgroup analysis, patients with adenocarcinoma had significantly worse OS and DFS compared with patients with SCC, regardless of treatment with radiotherapy alone or CCRT.ConclusionThe present study demonstrated that patients with adenocarcinoma of the cervix had poorer OS and DFS than patients with SCC, regardless of treatment with radiotherapy alone or CCRT. New treatment approaches should be considered for cervical adenocarcinoma.