All-perovskite tandem solar cells with 3D/3D bilayer perovskite heterojunction.

All-perovskite tandem solar cells promise higher power-conversion efficiency (PCE) than single-junction perovskite solar cells (PSCs) while maintaining a low fabrication cost1-3. However, their performance is still largely constrained by the subpar performance of mixed lead-tin (Pb-Sn) narrow-bandgap (NBG) perovskite subcells, mainly because of a high trap density on the perovskite film surface4-6. Although heterojunctions with intermixed 2D/3D perovskites could reduce surface recombination, this common strategy induces transport losses and thereby limits device fill factors (FFs)7-9. Here we develop an immiscible 3D/3D bilayer perovskite heterojunction (PHJ) with type II band structure at the Pb-Sn perovskite-electron-transport layer (ETL) interface to suppress the interfacial non-radiative recombination and facilitate charge extraction. The bilayer PHJ is formed by depositing a layer of lead-halide wide-bandgap (WBG) perovskite on top of the mixed Pb-Sn NBG perovskite through a hybrid evaporation-solution-processing method. This heterostructure allows us to increase the PCE of Pb-Sn PSCs having a 1.2-µm-thick absorber to 23.8%, together with a high open-circuit voltage (Voc) of 0.873 V and a high FF of 82.6%. We thereby demonstrate a record-high PCE of 28.5% (certified 28.0%) in all-perovskite tandem solar cells. The encapsulated tandem devices retain more than 90% of their initial performance after 600 h of continuous operation under simulated one-sun illumination.

Evaluating Lead Halide Perovskite Nanocrystals as a Spin Laser Gain Medium.

Spin-polarized charge endows conventional lasers with not only new functionalities but also reduced lasing thresholds thanks to the lifting of spin degeneracy. II-VI and III-V semiconductors have been extensively investigated as spin laser gain mediums; however, the degree of polarization is limited by the light hole and heavy hole degeneracy. Herein, we evaluate the potential of CsPbBr3 nanocrystals─ones that are featured with low band-edge degeneracy and therefore a high degree of polarization as a result of inverted band structure and large spin-orbit coupling─as a gain medium for spin lasers. Our experiment and numerical modeling results reveal that, within the spin relaxation lifetime, the optical gain threshold can be depressed by polarizing the charge using circularly polarized photoexcitation. However, prolonging the spin relaxation lifetime is required to realize a spin laser.

Efficient All-Perovskite Tandem Solar Cells with Low-Optical-Loss Carbazolyl Interconnecting Layers.

Combining wide-band gap (WBG) and narrow-band gap (NBG) perovskites with interconnecting layers (ICLs) to construct monolithic all-perovskite tandem solar cell is an effective way to achieve high power conversion efficiency (PCE). However, optical losses from ICLs need to be further reduced to leverage the full potential of all-perovskite tandem solar cells. Here, metal oxide nanocrystal layers anchored with carbazolyl hole-selective-molecules (CHs), which exhibit much lower optical loss, is employed to replace poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT : PSS) as the hole transporting layers (HTLs) in lead-tin (Pb-Sn) perovskite sub-cells and ICLs in all-perovskite tandem solar cells. Optically transparent indium tin oxide nanocrystals (ITO NCs) layers are employed to enhance anchoring of CHs, while a mixture of two CHs is adopted to tune the surface energy-levels of ITO NCs. The optimized mixed Pb-Sn NBG perovskite solar cells demonstrate a high PCE of 23.2 %, with a high short-circuit current density (Jsc ) of 33.5 mA cm-2 . A high PCE of 28.1 % is further obtained in all-perovskite tandem solar cells, with the highest Jsc of 16.7 mA cm-2 to date. Encapsulated tandem solar cells maintain 90 % of their reference point after 500 h of operation at the maximum power point (MPP) under 1-Sun illumination.

Bulk-like ZnSe Quantum Dots Enabling Efficient Ultranarrow Blue Light-Emitting Diodes.

Blue-emitting heavy-metal free QDs simultaneously exhibiting photoluminescence quantum yield close to unity and narrow emission line widths are essential for next-generation electroluminescence displays, yet their synthesis is highly challenging. Herein, we develop the synthesis of blue-emitting QDs by growing a thin shell of ZnS on ZnSe cores with their size larger than bulk Bohr diameter. The bulk-like size of ZnSe cores enables the emission to locate in the blue region with a narrow emission width close to its intrinsic peak width. The obtained bulk-like ZnSe/ZnS core/shell QDs display high quantum yield of 95% and extremely narrow emission width of ∼9.6 nm. Moreover, the bulk-like size of ZnSe cores reduces the energy level difference between QDs and adjacent layers in LEDs and improves charge transport. The LEDs fabricated with these high-quality QDs show bright pure blue emission with an external quantum efficiency of 12.2% and a relatively long operating lifetime.

CRISPR/Cas9-mediated sheep MSTN gene knockout and promote sSMSCs differentiation.

Myostatin (MSTN) is an important gene involved in the regulation of embryonic muscle cells and adult muscle development; it has a good application prospect in transgenic animal production by improving the yield of muscle. The purpose of this study is to construct MSTN gene knockout vector using clustered regularly interspaced short palindromic repeats ( CRISPR)/CRISPR-associated protein 9 ( Cas9). The knockout efficiency was evaluated in sheep ear fibroblasts (SEFs) by cleavage activity of transcription of guide RNA ( gRNA), luciferase-single-strand annealing assay, T7 endonuclease I assay (T7E1), and TA clone sequence (10/38); and above all, detection showed that the cleavage activity of CRISPR/Cas9-mediated MSTN reached 29%. MSTN-Cas9/gRNA4 was transfected into sheep skeletal muscle satellite cell (sSMSC) to confirm the function of MSTN in myotomes formation induced by starvation in low-serum medium. The results showed that myotubes formation efficiency were 11.2 ± 1.3% and 19.5 ± 2.1% in the control group and knockout group, respectively. The average length of myotomes was 22 ± 5.3 and 47 ± 3.6 µm, displaying that MSTN knockout can promote sSMSC differentiation in number and length. The unlabeled MSTN-Cas9/gRNA4 was transfected into SEFs and monoclonal positive cells was obtained after 48 hours transfection. The MSTN-positive cells were used as donor cells to perform somatic cell nuclear transplantation to produce transgenic sheep. A total of 20 embryos were transplanted into surrogate mothers, four of them normally produce offspring. The genomic DNA of surviving lambs were used as a template, three positive individuals were identified by T7E1 digestion. All the results demonstrated that the CRISPR/Cas9 system has the potential to become an important and applicable gene engineering tool in animal breeding.

Crucial genes and pathways in chicken germ stem cell differentiation.

Male germ cell differentiation is a subtle and complex regulatory process. Currently, its regulatory mechanism is still not fully understood. In our experiment, we performed the first comprehensive genome and transcriptome-wide analyses of the crucial genes and signaling pathways in three kinds of crucial cells (embryonic stem cells, primordial germ cell, and spermatogonial stem cells) that are associated with the male germ cell differentiation. We identified thousands of differentially expressed genes in this process, and from these we chose 173 candidate genes, of which 98 genes were involved in cell differentiation, 19 were involved in the metabolic process, and 56 were involved in the differentiation and metabolic processes, like GAL9, AMH, PLK1, and PSMD7 and so on. In addition, we found that 18 key signaling pathways were involved mainly in cell proliferation, differentiation, and signal transduction processes like TGF-ß, Notch, and Jak-STAT. Further exploration found that the candidate gene expression patterns were the same between in vitro induction experiments and transcriptome results. Our results yield clues to the mechanistic basis of male germ cell differentiation and provide an important reference for further studies.

A self-protection phenomenon in the Nafion membrane when it breathes in methanol-saturated air.

Ex situ characterizations based on TGA and XRD techniques revealed that MeOH vapor had little influence on the Nafion microstructures. To reveal the underlying mechanism, in this study, we designed new FTIR-based equipment to track in situ the microstructural changes of a bulk Nafion membrane in MeOH-saturated air. First, an interesting MeOH-breathing phenomenon was found in the ionic domains of Nafion. It demonstrated that there existed a dynamic equilibrium between the sorption and desorption processes of MeOH vapor in Nafion. Second, the FTIR results also detected the high stability of the hydrophobic regions of Nafion in MeOH vapor. The super-acid -CF2-SO3H always retained a small quantity of bonded H2O (H(+)(H2O)n) inside the Nafion membrane. MeOH vapor was absorbed first into the hydrophilic regions, however, the interactions between -CF2-SO3H and MeOH vapor were much weaker than those between -CF2-SO3H and H(+)(H2O)n. Therefore, a protective layer composed of residual water formed in the lumen of the hydrophilic ionic domains of Nafion, which protected its hydrophobic regions from the MeOH attack. Hereby, the self-protection ability of Nafion in MeOH vapor was detected for the first time. This work gave a new insight into the complex interplay between Nafion and MeOH vapor.

Does thermal treatment merely make a H2O-saturated Nafion membrane lose its absorbed water at high temperature?

Investigating the dehydration process of a Nafion membrane helps to understand the mechanism of the decrease in its proton conductivity under high-temperature and low-humidity conditions. Herein, the influence of thermal treatment on a H2O-saturated Nafion membrane was in situ studied by FTIR spectroscopy. With the aid of generalized two-dimensional correlation spectroscopy (2Dcos), the microstructural changes during the thermal treatment were discussed in detail. In short, side-chain regions first lost H2O, followed by the H2O loss in ionic cluster domains. It resulted in shrunken ionic channels in the Nafion membrane, which exhibited a negative influence on its proton conduction. The immediate aftermath was the crystallization of amorphous backbone regions. All these results were confirmed by TGA and XRD techniques, and the 2Dcos method was first applied in TGA and XRD results in this field.

Activity analysis and preliminary inducer screening of the chicken DAZL gene promoter.

This study was aimed at identifying the active control area of chicken DAZL gene core promoter, to screen optimum inducers of the DAZL gene, thus to enhance the differentiation of embryonic stem cells into spermatogonial stem cells. Fragments of chicken DAZL gene promoter were cloned into fluorescent reporter plasmids and transfected into DF-1 cells. Then Dual-Luciferase® Reporter Assay System was used to identify the activity of the DAZL gene under different inducers. Our studies showed that the DAZL core promoter region for the Suqin yellow chicken was -383 to -39 bp. The dual-luciferase® reporter showed that all-trans retinoic acid (ATRA), a retinoic acid receptor alpha agonist (tamibarotene/Am80), or estradiol (E2) could significantly enhance DAZL transcription. The in vitro inductive culture of chicken ESCs demonstrated that, with ATRA treatment, DAZL transcription peaked at 6 days and then decreased slowly; whereas, DAZL transcription was continuous and peaked at 10 days with Am80 treatment. E2 treatment significantly increased DAZL expression after 8 days. All three treatments were associated with the appearance of male germ cell (MGC)-like cells on day 10. These results provide the optimum inducer screening of the DAZL gene and lay the foundation for further screening of compounds that can induce the differentiation of ESCs into MGCs in vitro.

Enhanced Spin Polarization from Biaxially Strained Colloidal Quantum Dots.

Electron and hole spin polarization is crucial for quantum dots to be used in spin lasers and quantum information processing. However, the degree of spin polarization in II-VI and III-V semiconductor quantum dots is low because of the degenerated valence band. Here, we increase the light and heavy hole degeneracy by introducing biaxial strain into CdSe-based quantum dots, enabling the degree of spin polarization to be increased from 20% to 50% under photoexcitation. The optical gain threshold measurement further reveals that the increase in polarization helps to reduce the gain threshold.

Cloning and functional verification of the CmHSP17.9 gene from chrysanthemum.

Small molecular heat shock proteins (sHSPs) belong to the HSP family of molecular chaperones. Under high-temperature stress, they can prevent the aggregation of irreversible proteins and maintain the folding of denatured proteins to enhance heat resistance. In this study, the CmHSP17.9-1 and CmHSP17.9-2 genes, which were cloned from chrysanthemum (Chrysanthemum×morifolium 'Jinba') by homologous cloning, had a complete open reading frame of 480 bp each, encoding 159 amino acids. The protein subcellular localization analysis showed that CmHSP17.9-1 and CmHSP17.9-2 were located in the cytoplasm and mostly aggregated in granules, especially around the nucleus. Real-time quantitative PCR (qRT-PCR) analysis showed that the relative expression level of the CmHSP17.9-1 and CmHSP17.9-2 genes was highest in the terminal buds of the chrysanthemum, followed by the leaves. CmHSP17.9-1 and CmHSP17.9-2 overex-pression vectors were constructed and used to transform the chrysanthemum; overexpression of these genes led to the chrysanthemum phenotypes being less affected by high-temperature, and the antioxidant capacity was enhanced. The results showed that chrysanthemum with overex-pression of the CmHSP17.9-1 and CmHSP17.9-2 genes had stronger tolerance than the wild type chrysanthemum after high-temperature treatment or some degree of heat exercise, and overex-pression of the CmHSP17.9-1 gene led to stronger heat resistance than that of the CmHSP17.9-2 gene, providing an important theoretical basis for the subsequent molecular breeding and pro-duction applications of chrysanthemum.

Economic burden attributable to healthcare-associated infections at western China hospitals: 6 Year, prospective cohort study.

OBJECTIVES: Healthcare-associated infections (HAIs) represent a major threat to patient safety and are associated with significant economic burden. Calculating the costs attributable to HAIs is challenging given the various sources of bias. Although HAIs as a reasonably preventable medical harm should have been closely linked to medical insurance incentives, there was little linkage between HAIs and medicare in western China owing to the lack of economic evaluation data. The present study aimed to generate estimates of the attributable costs associated with HAIs and the magnitude of costs growth. METHODS: In this cohort study designed horizontally and vertically from 2016 to 2022, we compared outcomes of randomly sampling patients with HAIs and individually matched patients without HAIs in two cohorts at a 6-year interval at 34 hospitals in western China. The primary outcome was the direct medical cost for the entire hospital stay, converted to US dollars ($ for the benchmark year), discounted at 3% annually, and estimated separately in the full analysis set (FAS) and the per protocol set (PPS). We used multiple linear regression to adjust the discounted costs and to assess subgroups effects within each cohort. We nested a dynamic vertical comparison of costs attributable to HAIs between the front and rear cohorts. RESULTS: A total of 230 patients with HAIs in 2016 and 204 patients with HAIs in 2022 were enrolled. After a 1:1 match, all 431 pairs were recruited as FAS, of which 332 pairs as PPS met all matching restrictions. Compared to the 2016 cohort in FAS, the patients with HAIs in 2022 had a significantly older age (64.40 ± 16.45 years), higher repeat hospitalization rate (65 [32.02%] of 203), and lower immune function (69 [33.99%] of 203). The discounted costs and adjusted-discounted costs for patients with HAIs in the 2022 cohort were found to be significantly higher than those of patients without HAIs (discounted costs: $5484.60 [IQR 8426.03] vs $2554.04(4530.82), P < 0.001; adjusted-discounted costs: $5235.90 [3772.12] vs $3040.21(1823.36), P < 0.001, respectively), and also higher than those of patients with HAIs in the 2016 cohort (discounted costs: $5484.60 [8426.03] vs $3553.00 [6127.79], P < 0.001; adjusted-discounted costs: $5235.90 [3772.12] vs $3703.82 [3159.14], P < 0.001, respectively). In vertical comparison of PPS, the incremental costs of the 2022 cohort are 1.48 times higher than those of the 2016 cohort ($964.63(4076.15) vs $652.43 [2533.44], P = 0.084). CONCLUSIONS: This meticulously designed study in western China has successfully and accurately examined the economic burden attributable to HAIs. Their rapidly increasing tendency poses a serious challenge to patients, hospitals, and the medical insurance. A closer linkage between HAIs and ongoing motivating system changes is urgently needed in western China.

Enhanced Proton Transfer in Proton-Exchange Membranes with Interconnected and Zwitterion-Functionalized Covalent Porous Material Structures.

Excellent proton-conductive accelerators are indispensable for efficient proton-exchange membranes (PEMs). Covalent porous materials (CPMs), with adjustable functionalities and well-ordered porosities, show much promise as effective proton-conductive accelerators. In this study, an interconnected and zwitterion-functionalized CPM structure based on carbon nanotubes and a Schiff-base network (CNT@ZSNW-1) is constructed as a highly efficient proton-conducting accelerator by in situ growth of SNW-1 onto carbon nanotubes (CNTs) and subsequent zwitterion functionalization. A composite PEM with enhanced proton conduction is acquired by integrating CNT@ZSNW-1 with Nafion. Zwitterion functionalization offers additional proton-conducting sites and promotes the water retention capacity. Moreover, the interconnected structure of CNT@ZSNW-1 induces a more consecutive arrangement of ionic clusters, which significantly relieves the proton transfer barrier of the composite PEM and increases its proton conductivity to 0.287 S cm-1 under 95 % RH at 90 °C (about 2.2 times that of the recast Nafion, 0.131 S cm-1 ). Furthermore, the composite PEM displays a peak power density of 39.6 mW cm-2 in a direct methanol fuel cell, which is significantly higher than that of the recast Nafion (19.9 mW cm-2 ). This study affords a potential reference for devising and preparing functionalized CPMs with optimized structures to expedite proton transfer in PEMs.

Unravelling intrinsic descriptors based on a two-stage activity regulation of bimetallic 2D c-MOFs for CO2RR.

The bimetallic 2D conductive MOFs of M1Pc-M2-O, possessing dual metal sites to realize flexible molecular-level structural modification, are brilliant catalysts for electrochemical CO2 reduction. However, the bimetallic centers bring about the complex regulatory mechanism of catalytic activity and obscure principles for catalyst design. Herein, systematical theoretical investigation unravels intrinsic descriptors to design favorable M1Pc-M2-O catalysts based on the discovered coarse-fine two-stage activity regulation mechanism. The reaction site controls the M-COOH distance of the key intermediate and therefore affects the reaction kinetics for the first stage of coarse regulation. The other metal site influents the d-band center of the reaction site and thus constitutes the second stage of fine regulation. The coarse and fine regulation are related to the valence electrons (V), electronegativity (E), and bond length (LM-N/O) between the metal and coordination atoms. The intrinsic descriptor ϕ = (4 × VM1 × (EM1 + EN/O)/EN/O + VM2 × (EM2 + EN/O)/EN/O) × LM1-N/O (with a coefficient ratio of 4 : 1) was eventually established and correlated well with the reported experiments. On this basis, the favorable catalysts CoPc-Zn-O and CoPc-Co-O were located. The research results could contribute to the diversity of bimetallic 2D c-MOFs in CO2RR.

Replication Study: The microRNA miR-34a inhibits prostate cancer stem cells and metastasis by directly repressing CD44.

As part of the Reproducibility Project: Cancer Biology, we published a Registered Report (Li et al., 2015), that described how we intended to replicate selected experiments from the paper 'The microRNA miR-34a inhibits prostate cancer stem cells and metastasis by directly repressing CD44' (Liu et al., 2011). Here we report the results. We found the microRNA, miR-34a, was expressed at twice the level in CD44+ prostate cancer cells purified from xenograft tumors (LAPC4 cells) compared to CD44- LAPC4 cells, whereas the original study reported miR-34a was underexpressed in CD44+ LAPC4 cells (Figure 1B; Liu et al., 2011). When LAPC4 cells engineered to express miR-34a were injected into mice, we did not observe changes in tumor growth or CD44 expression; however, unexpectedly miR-34a expression was lost in vivo. In the original study, LAPC4 cells expressing miR-34a had a statistically significant reduction in tumor regeneration and reduced CD44 expression compared to control (Figure 4A and Supplemental Figures 4A,B and 5C; Liu et al., 2011). Furthermore, when we tested if miR-34a regulated CD44 through binding sites in the 3'UTR we did not find a statistically significant difference, whereas the original study reported miR-34a decreased CD44 expression that was partially abrogated by mutation of the binding sites in the CD44 3'UTR (Figure 4D; Liu et al., 2011). Finally, where possible, we report meta-analyses for each result.

In situ study of diffusion and interaction of water and mono- or divalent anions in a positively charged membrane using two-dimensional correlation FT-IR/attenuated total reflection spectroscopy.

Two-dimensional (2D) correlation analysis based on time-resolved FT-IR/attenuated total reflection (ATR) spectroscopy has been used to study the diffusion behavior of water and mono- or divalent anions in the positively charged membranes of different charge density. In 2D FT-IR/ATR spectra, the splitting of the water delta(OH) bending band in the spectral range 1700-1500 cm-1 indicates that there are three different states of water in the positively charged membrane, that is, the water molecules forming strong or weak hydrogen bonds with hydrophilic groups of the membrane and water molecularly dispersed with weaker hydrogen bonds. The wavenumber difference of the delta(OH) band in the low- and high-charge-density membrane indicates that water molecules form much stronger hydrogen bonds with hydrophilic groups in the high-charge-density membrane. The sequential order of the three water bands intensity changes shows that, in the process of water diffusion into the high-charge-density membrane, the hydrogen-bonding interaction between hydrophilic groups of the membrane and water molecules takes place gradually due to the highly cross-linked network structure of the membrane; in the process of water diffusion into the low-charge-density membrane, the strong hydrogen-bonding interaction between hydrophilic groups of the membrane and water molecules takes place instantaneously and this type of water easily diffuses due to the weak interactions between the water molecules and the membrane polymer. Furthermore, the diffusion processes of the electrolyte solution such as NaAc and Na2SO4 aqueous solutions in the positively charged membrane have also been examined.

The Presence of Cu Facilitates Adsorption of Tetracycline (TC) onto Water Hyacinth Roots.

Batch experiments were conducted to investigate the adsorption characteristics of tetracycline (TC), and the interactive effects of copper (Cu) on the adsorption of TC onto water hyacinth roots. TC removal efficiency by water hyacinth roots was ranging from 58.9% to 84.6%, for virgin TC, 1:1 TC-Cu and 1:2 TC-Cu. The Freundlich isotherm model and the pseudo-second-order kinetic model fitted the adsorption data well. Thermodynamics parameters ΔG° for TC were more negative in the TC plus Cu than the TC-only treatments, indicating the spontaneity of TC adsorption increased with increasing of Cu concentrations. An elevated temperature was associated with increasing adsorption of TC by water hyacinth roots. The additions of Cu(II) significantly increased TC adsorption onto water hyacinth roots within the pH range 4 to 6, because copper formed a strong metal bridge between root surface and TC molecule, facilitating the adsorption of TC by roots. However, Cu(II) hindered TC adsorption onto water hyacinth roots on the whole at pH range from 6⁻10, since the stronger electrostatic repulsion and formation of CuOH⁺ and Cu(OH)2. Therefore, the interaction between Cu(II) and TC under different environmental conditions should be taken into account to understand the environmental behavior, fate, and ecotoxicity of TC.

Novel Composite Proton Exchange Membrane with Connected Long-Range Ionic Nanochannels Constructed via Exfoliated Nafion-Boron Nitride Nanocomposite.

Nafion-boron nitride (NBN) nanocomposites with a Nafion-functionalized periphery are prepared via a convenient and ecofriendly Nafion-assisted water-phase exfoliation method. Nafion and the boron nitride nanosheet present strong interactions in the NBN nanocomposite. Then the NBN nanocomposites were blended with Nafion to prepare NBN Nafion composite proton exchange membranes (PEMs). NBN nanocomposites show good dispersibility and have a noticeable impact on the aggregation structure of the Nafion matrix. Connected long-range ionic nanochannels containing exaggerated (-SO3-)n ionic clusters are constructed during the membrane-forming process via the hydrophilic and H-bonding interactions between NBN nanocomposites and Nafion matrix. The addition of NBN nanocomposites with sulfonic groups also provides additional proton transportation spots and enhances the water uptake of the composite PEMs. The proton conductivity of the NBN Nafion composite PEMs is significantly increased under various conditions relative to that of recast Nafion. At 80 °C-95% relative humidity, the proton conductivity of 0.5 NBN Nafion is 0.33 S·cm-1, 6 times that of recast Nafion under the same conditions.

Two-Dimensional Zeolitic Imidazolate Framework/Carbon Nanotube Hybrid Networks Modified Proton Exchange Membranes for Improving Transport Properties.

Metal-organic framework (MOF)/polymer composite proton exchange membranes (PEMs) are being intensively investigated due to their potentials for the systematic design of proton-conducting properties. However, the development of MOF/polymer composite PEMs possessing high selectivity remains exceedingly desirable and challenging for practical application. Herein, two-dimensional (2D) zeolitic imidazolate framework (ZIF-8)/carbon nanotube (CNT) hybrid cross-linked networks (ZCN) were synthesized via the rational design of the physical form of ZIF-8, and then a series of composite PEMs were prepared by hybridizing ZCN with sulfonated poly(ether ether ketone) (SPEEK) matrix. The effect of the incorporation of zero-dimensional (0D) raw ZIF-8 nanoparticles and 2D ZCN on the proton conduction and methanol permeability of the composite membranes was systemically studied. Benefiting from the morphological and compositional advantages of ZCN, the SPEEK/ZCN composite membranes displayed a significant enhancement in proton conductivity under various conditions. In particular, the proton conductivity of SPEEK/ZCN-2.5 membrane was up to 50.24 mS cm-1 at 120 °C-30% RH, which was 11.2 times that of the recast SPEEK membrane (4.50 mS cm-1) and 2.1 times that of SPEEK/ZIF membrane (24.1 mS cm-1) under the same condition. Meanwhile, the methanol permeability of the SPEEK/ZCN composite membranes was greatly reduced. Therefore, novel MOF/polymer composite PEMs with high selectivity were obtained. Our investigation results reveal that the proton conductivity and methanol permeability of the MOF/polymer composite membranes can be effectively tailored via creating more elaborate superstructures of MOFs rather than altering the chemical component. This effective strategy may provide a useful guideline to integrate with other interesting MOFs to design MOF/polymer composite membranes.

Novel Slightly Reduced Graphene Oxide Based Proton Exchange Membrane with Constructed Long-Range Ionic Nanochannels via Self-Assembling of Nafion.

A facile method to prepare high-performance Nafion slightly reduced graphene oxide membranes (N-srGOMs) via vacuum filtration is proposed. The long-range connected ionic nanochannels in the membrane are constructed via the concentration-dependent self-assembling of the amphiphilic Nafion and the hydrophilic-hydrophobic interaction between graphene oxide (GO) and Nafion in water. The obtained N-srGOM possesses high proton conductivity, and low methanol permeability benefitted from the constructed unique interior structures. The proton conductivity of N-srGOM reaches as high as 0.58 S cm-1 at 80 °C and 95%RH, which is near 4-fold of the commercialized Nafion 117 membrane under the same condition. The methanol permeability of N-srGOM is 2.0 × 10-9 cm2 s-1, two-magnitude lower than that of Nafion 117. This novel membrane fabrication strategy has proved to be highly efficient in overcoming the "trade-off" effect between proton conductivity and methanol resistance and displays great potential in DMFC application.