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The rapidly increasing demand for clean and efficient energy devices is a critical issue for the sustainable development of human society. The green and low-cost aqueous zinc–air batteries (ZABs) w...

Tuning the electronic states near the Fermi level can effectively facilitate the reaction kinetics. However, elucidating the role of a specific electronic state of metal oxide in simultaneously regulating the CO 2 electroreduction reaction (CO 2 RR) and competing hydrogen evolution reaction (HER) is still rare, making it difficult to accurately predict the practical CO 2 RR performance. Herein, replacing the Zn site by heteroatoms with different outer electrons (Mo and Cu) is found to tune both occupied and unoccupied orbitals near the Fermi level of ZnO. Moreover, the different electronic states significantly modulate both CO 2 RR and HER activity with a totally inverse trend, thus dramatically tuning the practical CO 2 RR performance. In parallel, the correlation between electronic states, reaction free energies and practical activity is demonstrated. This work provides a possibility for engineering efficient CO 2 RR eletrocatalysts through tunable composition and electronic structures.

As one of the most promising energy storage systems, conventional lithium-ion batteries based on the organic electrolyte have posed challenges to the safety, fabrication, and environmental friendliness. By virtue of the high safety and ionic conductivity of water, aqueous lithium-ion battery (ALIB) has emerged as a potential alternative. Whereas, the narrow electrochemical stability window (ESW) of water severely restricts the performance of ALIB. In recent years, with the introduction of water-in-salt electrolyte (21 mol LiTFSI in 1 kg H2O), the ESW of aqueous electrolyte was expanded to ~3 V, which significantly improved the voltage and energy density of ALIBs. Nevertheless, in view of such high salt concentration, water-in-salt electrolyte will dramatically increase the cost of ALIBs. Hence, due to their lower cost and abundant resource, aqueous sodium-ion batteries and zinc-based batteries show great potential. Herein, the latest advances of water-in-salt electrolyte in aqueous rechargeable batteries are briefly reviewed. Some challenges and prospects of water-in-salt electrolyte are also discussed to broaden the horizons for future development.

The rational design and controllable synthesis of excellent bifunctional oxygen reduction and evolution reaction (ORR/OER) electrocatalysts are of vital importance for zinc–air battery applications. Herein, we report nitrogen/sulfur-codoped carbon nanosheets (NSC) decorated with dense Co9S8/Co1−xS heterostructures (Co9S8/Co1−xS@NSC), prepared by a one-pot salt template-assisted pyrolysis procedure. The population of the Co9S8/Co1−xS heterostructure can be effectively controlled by tuning the precursor components. Salt templates constructed hierarchical porosity for the wide-open carbon nanosheets, which maximized the N functional groups to anchor highly dispersive Co9S8/Co1−xS species. Experiments and theoretical simulations revealed notable electronic interactions within Co9S8/Co1−xS interfaces, which can effectively optimize the adsorption/desorption behaviors of intermediates in ORR/OER, thus promoting the bifunctional electrocatalytic performance. The half-wave potential for the ORR of 0.86 V and the OER electrocatalytic potential of 1.52 V at 10 mA cm−2 were obtained. Benefiting from the strong coupling effect between the Co9S8/Co1−xS species and the carbon substrate, superior durability was obtained for 2000 ORR/OER cycles. The practical zinc–air battery based on the Co9S8/Co1−xS@NSC cathode manifested a high open-circuit voltage, small voltage gap and robust reversibility. Our study revealed the great potential of the bi-elemental (Co and S) heterostructure in enhancing the ORR/OER activity, which suggests a logical extension to other electrocatalysis systems.

The development of efficient and low-cost flexible metal electrodes is significant for flexible rechargeable zinc-air batteries (ZABs). Herein, we reported a new type of flexible metal (zinc and nickel) electrode fabricated

Cytogenetic abnormalities are powerful prognostic factors in multiple myeloma (MM) and are routinely analyzed by FISH on bone marrow (BM) plasma cells (PC). Although considered the gold standard, FISH experiments can be laborious and expensive. Therefore, array-CGH (aCGH) has been introduced as an alternative approach for detecting copy number aberrations (CNA), reducing the number of FISH experiments per case and yielding genome-wide information. Currently, next generation sequencing (NGS) technologies offer new perspectives for the diagnostic workup of malignant disorders. In this study, we examined ultra-low depth whole genome sequencing (LDS) as a valid alternative for aCGH for the detection of CNA in BM PC in MM. To this end, BM aspirates obtained in a diagnostic setting from 20 MM cases were analyzed. CD138+ cell-sorted samples were subjected to FISH analysis. DNA was extracted for subsequent aCGH and LDS analysis. CNA were detected by aCGH and LDS in all but one case. Importantly, all CNA identified by parallel first generation aCGH analysis were also detected by LDS, along with six additional CNA in five cases. One of these additional aberrations was in a region of prognostic importance in MM and was confirmed using FISH. However, risk stratification in these particular cases was unaffected. Thus, a perfectly concordant prognostication between array-CGH and LDS was observed. This validates LDS as a novel and cost-efficient tool for the detection of CNA in MM. ispartof: GENES CHROMOSOMES & CANCER vol:59 issue:8 pages:465-471 ispartof: location:United States status: published

Thin-felt ZSM-11/stainless-steel(SS)-fiber composites are successfully prepared via a combined washcoating and steam-assisted crystallization (SAC) method. Pre-aging of synthesis sol at a lower temperature of 80 °C can facilitate the zeolite nucleation and subsequent SAC growth at 180 °C. Such synthesis approach realizes the flexible tuning of acidity via adjusting SiO2/Al2O3 molar ratio in a wide range, including but not limited from 105 to 425. The as-synthesized ZSM-11/SS-fiber composites are employed as catalysts for the methanol-to-propylene reaction, and the promising thin-felt catalyst with SiO2/Al2O3 molar ratio of 200 shows remarkable stability improvement in comparison with its powdered counterpart, due to enhanced zeolite utilization efficiency and heat/mass transfer by the microfibrous-structured design.

Energy and environmental issues received widespread attentions due to the fast growth of world population and rapid development of social economy. As a transition metal dichalcogenide, tungsten disulfide (WS2) nanomaterials make important research progress in the field of energy conversion and storage. In view of the versatile and rich microstructure of these materials, the modification and controllable synthesis of WS2 nanomaterials also inspire a research interest. This review mainly focuses on WS2-based nanomaterials in the application of energy conversion and storage as well as discusses some basic characteristics and modification strategies of them. Finally, the research progress of WS2-based nanomaterials is reviewed and some prospects for future research directions are proposed. This review is expected to be beneficial to the future study of WS2 nanomaterials used in the field of energy conversion and storage.

Aqueous battery systems feature high safety, but they usually suffer from low voltage and low energy density, restricting their applications in large-scale storage. Here, we propose an electrolyte-decoupling strategy to maximize the full potential of Zn–MnO2 batteries by simultaneously enabling the optimal redox chemistry of both the Zn and MnO2 electrodes. The decoupled Zn–MnO2 battery exhibits an open-circuit voltage of 2.83 V (in contrast to the typical voltage of 1.5 V in conventional Zn–MnO2 batteries), as well as cyclability with only 2% capacity fading after deep cycling for 200 h. Benefiting from the full utilization of MnO2, the Zn–MnO2 battery is also able to maintain approximately 100% of its capacity at various discharge current densities. We also demonstrate the feasibility of integrating the Zn–MnO2 battery with a wind and photovoltaic hybrid power generating system. This electrolyte-decoupling strategy is shown to be applicable for other high-performance zinc-based aqueous batteries such as Zn–Cu and Zn–Ag batteries. Low energy density and limited cyclability are preventing the commercialization of aqueous Zn–MnO2 batteries. Here, the authors combine the merits of operating Zn anodes in alkaline conditions and MnO2 cathodes in acidic conditions, via an electrolyte-decoupling strategy, to realize high-performance batteries.

Developing superior electrocatalysts for formic acid oxidation (FAO) is the most crucial step in commercializing direct formic acid fuel cells. Herein, we electrodeposited palladium membranes with periodically ordered mesoporosity obtained by asymmetrically replicating the bicontinuous cubic phase structure of a lyotropic liquid-crystal template. The Pd membrane with the largest periodicity and highest degree of order delivered up to 90.5 m2 g-1 of electrochemical active surface area and 3.34 A mg-1 electrocatalysis capability towards FAO, 3.8 and 7.8 times the values of the commercial Pd/C catalyst, respectively. By controlling the temperature and potential of the electrodeposition procedure, the periodicity area and order degree of the mesoporosity are highly tunable. These Pd membranes gave prototype formic acid fueled cells with 4.3 and 2.4 times the maximum current and power density of the commercial Pd/C catalyst.

Renewable arenes and aromatic alcohols can be derived from lignocellulose by biorefineries, which has been considered as a sustainable alternative to replace petrochemical feedstocks in the synthesis of monobenzylation products, key industrial intermediates, via benzylation reactions. Zeolites with micropores are the most widely used catalysts in the benzylation of arenes, however, their performance suffers from diffusion limitations in converting large arenes. In this work, mesoporous and microporous H–Beta zeolites were prepared and applied in the systematic study of benzylation of arenes (benzene, toluene, p-xylene and mesitylene) with benzyl alcohol (BA). The porous structure of these zeolites has been confirmed by XRD, BET and TEM techniques. The catalytically active Bronsted acid sites (BAS) were determined by quantitative 1H magic-angle spinning (MAS) nuclear magnetic resonance (NMR) experiments. The benzylation studies have shown that introducing mesopores into H–Beta zeolites can significantly increase the diffusion/access of arenes to surface sites, particularly for bulky arenes (e.g. mesitylene), while micropores are mainly selective for the conversion of small arenes (e.g. benzene). Increasing the nucleophilicity of arenes with more alkyl groups can enhance their catalytic performance in mesopores, however, the increase hinders their conversion in micropores because of the shape selectivity due to their increasing molecular size. Compared to mesopores, micropores promote the conversion of small arenes (e.g. benzene), which can be additionally enhanced by a high Bronsted acidity. Therefore, introducing a suitable porosity balanced with acidity are keys in the tailoring of the catalytic performance of H-Beta zeolites for target benzylation reactions.

The presence of potentially toxic metals in water causes a strong impact on environment and human health. In this study, activated biochar was produced by using chemical oxidation method from wheat straw as natural adsorbent and was employed for heavy metals competitive remediation. The morphology, structure, and chemical properties of biochar before and after adsorption were characterized by FTIR, XRD, SEM and EDX mapping techniques. The competitive adsorption efficiency of adsorbent for divalent cadmium (Cd) and lead (Pb) from contaminated water was investigated by using wide range of several initial metal concentration, contact time and pH. Maximum adsorption of Cd(II) and Pb(II) was found in the pH range of 6–8. The adsorption capacity for Cd(II) and Pb(II) was 8.85 and 9.03 mg/g, respectively. Thermodynamics parameters and kinetic models were applied to adsorption data. The isotherm data followed Langmuir model, corresponding to monolayer adsorption of the two ions in the contaminated water. The kinetic data followed the pseudo 2nd order kinetics model, which authenticates the chemisorption nature. The thermodynamic study indicated that Cd adsorption is a spontaneous exothermic process while Pb adsorption is an endothermic process. Mineral precipitation, surface complexation, and cation-π interactions are the major remediation strategies for Cd(II) and Pb(II).

Batteries are considered as an attractive candidate for grid-scale energy storage systems (ESSs) application due to their scalability and versatility of frequency integration, and peak/capacity adjustment. Since adding ESSs in power grid will increase the cost, the issue of economy, that whether the benefits from peak cutting and valley filling can compensate for the cost input of adding energy storage system or not, is particularly concerned. Here we show how the cost of battery deployment can potentially be minimized by carrying out an economic assessment for the cases of different batteries applied in ESSs. To make this analysis, we develop a techno-economic model and apply it to the cases of ESSs with batteries in applications. Our results show that batteries could be attractive for investors even now if appropriate batteries are selected for ESSs applications. Valve regulated lead acid batteries has a lower cost of initial investment, which is suitable for the situations that are sensitive to the initial investment cost. Lithium iron phosphate (LiFePO4, LFP) battery can be applied in the situations with a high requirement for service life. While zinc-air batteries still have great application prospects to cope with resource depletion due to excellent performance, low cost and low pollution. The current policy debate should therefore be refocused so as to promote technological development and to encompass the removal of such barriers.

Considering the environmental problems caused by a large amount of cotton textile waste and its possible applications in flexible electrodes, it is very promising to reuse the cotton textile waste as an electrode material, reducing the cost of flexible electrodes and alleviating environmental problems. In this work, we present a rechargeable flexible Zn-air battery based on cotton textile waste, which employs Ni-metallized cotton textile waste (NMCTW) as a flexible substrate for Zn anodes and air cathodes. The transparent NiFe hydroxide thin film horizontally grown on the surface of the NMCTW substrate was synthesized in situ by the electrodeposition method, which exhibits excellent catalytic activity because of the high surface area of the two-dimensional (2D) thin film, large contact area between the thin film and substrate, and fast charge transport of the 2D thin-film structure. In view of the high catalytic performance of the NiFe hydroxide thin film, it was used as the catalytic material of the air cathode for the flexible Zn-air battery. The assembled Zn-air battery based on cotton textile waste demonstrated a good rate performance and outstanding charge and discharge cycling stability. The assembled Zn-air battery was applied to power the light-emitting diode, which exhibits exceptional flexibility and stable output power even under severe mechanical bending deformation, proving the feasibility for its application in flexible electronics.

Dry reforming of methane (DRM) is a promising chemical approach to convert greenhouse gases CO2 and CH4 into valuable fuels. Previous experimental study has shown that the addition of alkaline eart...

Alkaline zinc–air batteries are promising energy storage technologies with the advantages of low cost, ecological friendliness, and high energy density. However, the rechargeable zinc–air battery has not been used on a commercial scale because the zinc electrode suffers from critical problems such as passivation, dendrite growth, and hydrogen evolution reaction, which limit the practical applications of zinc–air batteries. Herein, the Perspective summaries the solutions to minimize the negative effects of zinc electrodes on discharge performance, cycling life, and shelf life. The future direction of academic research based on current studies of the existing challenges is proposed.

Flexible zinc-air batteries (ZABs) have been considered as one of the most outstanding energy storage devices for flexible and portable electronics because of their superior energy density and environmental friendliness. As the "blood" of flexible ZABs, electrolytes play a significant role in determining their performance, such as discharge working time, cycling property, and shelf life. Herein, a novel polymer electrolyte based on quaternary ammonium hydroxides is first applied in flexible zinc-air batteries. Tetraethylammonium hydroxide (TEAOH) is innovatively used as the ionic conductor with poly(vinyl alcohol) (PVA) as the polymer host in the polymer electrolyte and exhibits a good water retention capability, resulting in not only a good shelf life but also a good working life of the flexible zinc-air batteries. The fabricated polymer electrolyte maintains its high ionic conductivity of 30 mS cm

Summary: CO2 circular economy is urgently calling for the effective large-scale CO2 reutilization technologies. The reverse water-gas shift (RWGS) reaction is the most techno-economically viable candidate for dealing with massive-volume CO2 via downstream mature Fischer-Tropsch and methanol syntheses, but the desired groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a nano-intermetallic InNi3C0.5 catalyst, for example, being particularly active, selective, and stable for the RWGS reaction. The InNi3C0.5(111) surface is dominantly exposed and gifted with dual active sites (3Ni-In and 3Ni-C), which in synergy efficiently dissociate CO2 into CO* (on 3Ni-C) and O* (on 3Ni-In). O* can facilely react with 3Ni-C-offered H* to form H2O. Interestingly, CO* is mainly desorbed at and above 400°C, whereas alternatively hydrogenated to CH3OH highly selectively below 300°C. Moreover, this nano-intermetallic can also fully hydrogenate CO-derived dimethyl oxalate to ethylene glycol (commodity chemical) with high selectivity (above 96%) and favorable stability. : Chemical Reaction; Catalysis; Nanomaterials Subject Areas: Chemical Reaction, Catalysis, Nanomaterials

A hollow-B-ZSM-5/SS-fiber catalyst is developed through alkali leaching of the full-silica core of the silicalite-1@B-ZSM-5 in situ structured onto a thin-felt stainless-steel fiber (20 μm SS-fiber), which is synthesized by a seed-assisted dry-gel vapor-phase transport method. As-obtained catalyst shows marked improvement in the mesoporosity-dependent diffusion (by o-xylene diffusion measurement). Boron incorporation is essential for preventing the framework dealumination during alkali leaching treatment due to the increased framework negative charges. The hollow-B-ZSM-5/SS-fiber catalyst shows remarkable stability improvement in the methanol-to-propylene (MTP) reaction because of the enhanced diffusion of the nano-hollow-structure and the boron-incorporation stabilized framework aluminum. A boron-free hollow-ZSM-5/SS-fiber is also obtainable with the textural properties comparable to the hollow-B-ZSM-5/SS-fiber but shows undesired degeneration of the tetra-coordinated aluminum. The preferential generation of coke in the micropores of the hollow-ZSM-5/SS-fiber causes a rapid deactivation even compared to the parent silicalite-1@ZSM-5/SS-fiber, due to the existence of extra-framework aluminum.

The rapid advancement of flexible and wearable electronic devices drives the need for flexible batteries, and zinc–air batteries (ZABs) have attracted extensive interest due to their extremely high theoretical energy density, eco-friendliness and low cost. However, the use of conventional alkaline ZABs is significantly restricted by corrosion and dendrite growth at the Zn anode and fast carbonate formation of the electrolyte. Herein, we report an emerging type of ZAB that uses a near-neutral gel polymer electrolyte (neutral GPE) with good water retention and high ionic conductivity; this ZAB system is more environmentally friendly and less corrosive than alkaline electrolytes, thus potentially avoiding carbonation problems and mitigating corrosion issues. Furthermore, an integrated nanoporous air cathode with an enlarged interfacial contact area and catalytic sites is utilized, and it demonstrates excellent flexibility and high strength. Due to these advantages, the assembled neutral GPE-based flexible ZABs exhibit a prolonged cycle life of 70 h in the fresh state and after being packaged for 10 days, indicating a remarkable battery life performance. Furthermore, the ZABs can be fabricated in customized shapes and sizes to satisfy the space and energy demands of a variety of applications, and they can operate without degraded battery performance under bending conditions and even during the tailoring process.

Highlights A unique dual-ion adsorption mechanism for zinc ion capacitor is enabled by a carbon cathode with defect-rich tissue, dense heteroatom dopant and immense surface area.The active sites on carbon surface for reversible dual-ion adsorption are identified by in-depth characterizations and DFT simulations.The zinc ion capacitor delivers unrivaled combination of high energy and power characteristics. The superb energy, power and cyclability are achieved in multiple cell configurations including coin cell and flexible solid-state pouch-/cable-type cells. Supplementary Information The online version of this article (10.1007/s40820-021-00588-5) contains supplementary material, which is available to authorized users., Aqueous zinc-based batteries (AZBs) attract tremendous attention due to the abundant and rechargeable zinc anode. Nonetheless, the requirement of high energy and power densities raises great challenge for the cathode development. Herein we construct an aqueous zinc ion capacitor possessing an unrivaled combination of high energy and power characteristics by employing a unique dual-ion adsorption mechanism in the cathode side. Through a templating/activating co-assisted carbonization procedure, a routine protein-rich biomass transforms into defect-rich carbon with immense surface area of 3657.5 m2 g−1 and electrochemically active heteroatom content of 8.0 at%. Comprehensive characterization and DFT calculations reveal that the obtained carbon cathode exhibits capacitive charge adsorptions toward both the cations and anions, which regularly occur at the specific sites of heteroatom moieties and lattice defects upon different depths of discharge/charge. The dual-ion adsorption mechanism endows the assembled cells with maximum capacity of 257 mAh g−1 and retention of 72 mAh g−1 at ultrahigh current density of 100 A g−1 (400 C), corresponding to the outstanding energy and power of 168 Wh kg−1 and 61,700 W kg−1. Furthermore, practical battery configurations of solid-state pouch and cable-type cells display excellent reliability in electrochemistry as flexible and knittable power sources. Supplementary Information The online version of this article (10.1007/s40820-021-00588-5) contains supplementary material, which is available to authorized users.

Since the Paris Agreement came into effect in 2016, governments worldwide have established goals for future carbon emission reduction. Enterprises and governments have begun to pay attention to the management of carbon emission. This study explored the dynamic relationship between business growth and carbon emission performance by constructing and using a time series model to predict the trend of carbon emission. The time series method (ADF unit root test, cointegration test and VAR model etc.) was adopted to investigate 805 companies listed on the Taiwan Stock Exchange from 2012 to 2017 as the sample of this study. The carbon emission performance variables include: total carbon emission, annual increase of carbon emission, and annual increase rate of carbon emission. The business growth variables include: growth rate, stability of growth, and years of establishment. The results showed a long-term dynamic relationship between business growth and carbon emission performance. Therefore, using the time series method can assist enterprises in developing green strategies, strengthen carbon emission prediction and management capacities, reduce operating costs and risks, and actively achieve the ideal of sustainable development.

A couple of molecular-targeting medications, such as Lenvatinib, are available for the treatment of hepatocellular carcinoma (HCC) in addition to Sorafenib in an advanced stage. Approval for the use of immune check-point inhibitors, such as Nivolumab and Pembrolizumab has shifted the paradigm of current HCC treatment, and the monotherapy or in combination with Lenvatinib or Sorafenib has significantly extended overall survival or progression-free survival in a large portion of patients. A combination of programmed cell death ligand-1 (PD-L1) inhibitor Atezolizumab with a vascular endothelial growth factor (VEGF) inhibitor, Bevacizumab, has recently achieved promising outcome in unresectable HCC patients. Other immunotherapy, such as chimeric antigen receptor T (CAR-T) cell therapy has achieved an evolutional success in hematologic malignancies, and has extended its use in deadly solid tumors, such as HCC. Although there exist various barriers, novel approaches are developed to move potential adoptive T cell therapy strategies, including cytokine-induced killer (CIK) cells, tumor-infiltrating lymphocytes (TIL), T cell receptor (TCR) T cells, CAR-T cells, to clinical application.

Bacillus utilize preferred sugars such as glucose over other carbon sources due to carbon catabolite repression (CCR). Surfactin is a small signal molecule to regulate the quorum-sensing (QS) response such as biofilm formation and sporulation in B. subtilis. Here, the srfA operon for synthesis of surfactin was mutated for disrupting the production of surfactin in B. amyloliquefaciens. The srfA-mutant strain showed a defective biofilm and sporulation but could be restored by addition with surfactin, indicating that surfactin is a QS signal molecule in B. amyloliquefaciens. Unexpectedly, mutation of srfA also led to the cells' death although nutrients were still enough to support the bacterial growth during this period. Analysis of transcriptomes found that the srfA-mutant strain could not relieve CCR to use non-preferred carbon sources after glucose exhaustion due to deficiency of surfactin. This was further verified by the fact that addition with glucose could dramatically restore the growth, and addition with surfactin could improve the enzymes' activity (e.g., glucanase and α-amylase) to use non-preferred carbon sources in the srfA-mutant strain. After glucose exhaustion, the cells produce surfactin to relieve CCR for utilizing non-preferred sugars. As a signal molecule to regulate QS, surfactin also directly or indirectly relieves the CcpA-mediated CCR to utilize non-preferred carbon sources countering nutrient limitation (e.g., glucose deprivation) in the environment. In conclusion, our findings provide the first evidence that the QS signal molecule of surfactin is also involved in relieving the CcpA-mediated CCR in B. amyloliquefaciens.

The presence of nanoplastics in drinking water inducing inevitable exposure to human beings has aroused considerable attention. It is worth evaluating the degradation and even mineralization of nanoplastics in drinking water treatment plants designed for guaranteeing drinking water safety. Herein we mainly focus on the decomposition of nano-sized polystyrene plastics by two commonly used disinfection techniques, namely ozonation and chlorination. At recommended dosage for disinfection, ozonation achieves 99.9% molecular weight (MW) degradation and 42.7% mineralization of nano-sized polystyrene plastics in 240 min, while chlorination only attains 7.1% MW degradation and 4.3% mineralization. The overwhelming MW degradation is concentrated in first 30 min with 96.3% for ozonation and 4.2% for chlorination. With the proceeding of ozonation, the surface of nano-sized polystyrene plastics becomes rough and the particle size is decreased, during which the introduction of oxygen-containing groups on the surface of nano-sized polystyrene plastics increases the hydrophilicity of plastics, thus contributing to the further oxidative degradation to produce formic acid, phenol, acetophenone, hydroquinone and other products. However chlorination cannot roughen the surface of nano-sized polystyrene plastics, and only destroys a small amount of C-C bonds in main chain to form shorter chains polymers. This finding shows ozonation other than chlorination is available and effective for degradation of nano-sized polystyrene plastics, indicating that ozonation could be employed as a potential technique to tackle nanoplastics pollution in drinking water treatment plants.

In this critical Review we focus on the evolution of the hybrid ion capacitor (HIC) from its early embodiments to its modern form, focusing on the key outstanding scientific and technological questions that necessitate further in-depth study. It may be argued that HICs began as aqueous systems, based on a Faradaic oxide positive electrode (e.g., Co3O4, RuOx) and an activated carbon ion-adsorption negative electrode. In these early embodiments HICs were meant to compete directly with electrical double layer capacitors (EDLCs), rather than with the much higher energy secondary batteries. The HIC design then evolved to be based on a wide voltage (∼4.2 V) carbonate-based battery electrolyte, using an insertion titanium oxide compound anode (Li4Ti5O12, LixTi5O12) versus a Li ion adsorption porous carbon cathode. The modern Na and Li architectures contain a diverse range of nanostructured materials in both electrodes, including TiO2, Li7Ti5O12, Li4Ti5O12, Na6LiTi5O12, Na2Ti3O7, graphene, hard carbon, soft carbo...

A series of thin-felt SS-fiber@HZSM-5 catalysts are fabricated via the seed-assisted vapor-phase transport (VPT) method. The crystal size and mesoporosity of zeolite shell are controllably tuned toward enhanced diffusion by increasing the silicalite-1 seeding gel (SG) amount used. The microstructured catalyst obtained with a high SG amount of 50% contains a smaller crystal size of ∼70 nm and higher mesopore volume of 0.21 cm3 gzeolite−1, which markedly prolonged single-run lifetime with a remarkable decrease in the coking rate in the MTP process. The adverse effect of non-uniform aluminum in the zeolite shell on the MTP stability is revealed. The use of aluminum-containing SG to replace the pure-silica one makes the acid sites of as-obtained ZSM-5 mounted on SS-fiber distributed homogeneously thereby leading to a marked suppression of hydrogen transfer, and as a result, the catalyst single-run lifetime is further increased by ∼40%. This promising SS-fiber@HZSM-5 catalyst is stable for at least 1600 h (>94% conv.) with a high propylene selectivity of ∼36% at 450 °C using a WHSV of 1 h−1 for a feed of MeOH/H2O molar ratio of 1:1, by taking advantage of improved diffusion from mesoporosity development and uniform aluminum distribution as well as our distinctive microfibrous-engineered design.

From macro- to nano-engineering of a promising CeO2-ZrO2-doped NiO-Al2O3/Ni-foam catalyst has been demonstrated for the oxidative dehydrogenation of ethane to ethylene (ODE), through facial wet chemical etching of a Ni-foam followed post modification with CeO2 and ZrO2. The NiO-Al2O3/Ni-foam (denoted as NANF) achieved a high ethane conversion of 25.2% but with a very low ethylene selectivity of 43.1% at 450 °C. ZrO2-doping of the NANF led to a remarkable improvement in the ethylene selectivity but serious deterioration of activity while the CeO2-doping showed an opposite effect. Co-doping of the NANF using optimal amount of CeO2 and ZrO2 markedly promoted not only the activity but also the selectivity to ethylene. For example, over the 1CeO2-5ZrO2-NANF (CeO2:1 wt%, ZrO2:5 wt%) catalyst, a high ethane conversion of 40.3% was obtained with a 60.6% ethylene selectivity for a feed gas of C2H6/O2/N2 = 1/1/8 at 500 °C and a gas hourly space velocity of 18,000 cm3 g−1 h−1, corresponding to a high ethylene productivity of 510 gEthylene kgcat−1 h−1. In nature, co-doping with CeO2 and ZrO2 synergistically tamed the NiO for selective H-abstraction of the ethane molecules other than over oxidation of them.

Surfactin, a lipopeptide produced by Bacillus species, has been used for the oral delivery of insulin. In this study, another lipopeptide of iturin was tested for its ability to orally delivery insulin alone or plus surfactin. Iturin could form co-precipitate with insulin at acidic pH values. After treatment by ultrasonification, the structure of coprecipitate was destroyed that led to a significant decrease in hypoglycemic effect after oral administration. Iturin weakly binds to (Kd = 257 μM) and induce insulin structure more compact that is favorable for insulin uptake by the intestine. After being coated with Acryl-Eze by lyophilization, the coprecipitate formed the spherical enteric-coated insulin microparticles delivered by iturin with a relative oral bioavailability of 6.84% in diabetic mice. For further improving oral hypoglycemic effect, surfactin was added to form the spherical enteric-coated insulin microparticles in a formulation containing insulin, Acryl-Eze, iturin and surfactin at a ratio of 1:1:0.5: 0.5 (w/w), with an insulin encapsulation efficiency of 66.22%. The enteric-coated insulin microparticles delivered by iturin plus surfactin showed a classical profile for controlled release in the intestine with a relative bioavailability of 7.67% after oral administration, which could effectively control the postprandial blood glucose at a level about 50% of the initial one just like the subcutaneous injection. Collectively, iturin plus surfactin is more efficient for oral delivering insulin than the sole one, and the resultant enteric-coated insulin microparticles are potential for the development of oral insulin to control postprandial blood glucose in diabetic patients.

CO2 electroreduction (CO2 RR) to CO is promising for the carbon cycle but still remains challenging. Au is regarded as the most selective catalyst for CO2 RR, but its high cost significantly hinders its industrial application. Herein, the bimetallic CuInSe2 is found to exhibit an Au-like catalytic feature: i) the interaction of Cu and In orbitals induces a moderate adsorption strength of CO2 RR intermediates and favors the reaction pathway; and ii) the hydrogen evolution is energetically unfavorable on CuInSe2 , as a surface reconstruction along with high energy change will occur after hydrogen adsorption. Furthermore, the Se vacancy is found to induce an electron redistribution, slightly tune the band structure, and optimize the CO2 RR route of bimetallic selenide. Consequently, the Se-defective CuInSe2 (V-CuInSe2 ) achieves a highly selective CO production ability that is comparable to noble metals in aqueous electrolyte, and the V-CuInSe2 cathode shows a satisfactory performance in an aqueous Zn-CO2 cell. This work demonstrates that designing cost-effective catalysts with noble-metal-like properties is an ideal strategy for developing efficient electrocatalysts. Moreover, the class of transition bimetallic selenides has shown promising prospects as active and cost-effective electrocatalysts owing to their unique structural, electronic, and catalytic properties.

As an important epigenetic modification, 5-hydroxymethylcytosine (5hmC) aroused wide concern about the distribution and the function. Due to the necessity of 5hmC detection, a novel photoelectrochemical (PEC) biosensor was established based on the in-situ generated heterojunction of Bi4NbO8Cl@Bi2S3, which was employed as the substrate material with excellent photoelectric property. The specific recognition of 5hmC relied on the covalent reaction between –CH2OH of 5hmC and –SH on the substrate electrode under the catalysis of M.HhaI methyltransferase. Afterwards, ZrO2 was used as signal amplification unit capturing by the specific reaction of Zr with the phosphate group of 5hmC. The experimental results demonstrated well specificity and sensitivity of this biosensor. Under optimal conditions, the linear relationship between the photocurrent and the logarithm value of 5hmC concentration was constructed with the range from 0.3 to 300 nM and the detection limit of 0.0779 nM (S/N = 3). The procedures of constructing this biosensor were compact and convenient, and this biosensor realized actual detection of 5hmC level in wheat sample. Significantly, this biosensor was applied to a preliminary study that the heavy metal Pb2+ and the perfluorooctanoic acid influence the expression of 5hmC in the genomic DNA of wheat seedling roots and leaves.

The endogenous epigenetic marker 5-formylcytosine (5 fC) is introduced by 5-methylcytosine (5 mC) oxidation under action of enzyme oxidation, and plays an important role in many life activities. Since the content of 5 fC in mammalian tissues and cells is very low, it is necessary to exploit a sensitive and specific detection method to further understand the function of 5 fC. In this work, a sensitively and selectively photoelectrochemical (PEC) biosensor was developed for 5-formyl-2′-deoxycytidine (5fdC) detection. CuBi2O4/ZnPc@WS2 was used as photoactive material, where the formed ternary heterojunction structure greatly enhanced the PEC response and increased the detection sensitivity. Positively charged polyethyleneimine (PEI) was employed as 5fdC recognition and capture unit, where the amine group on PEI specifically reacted with aldehyde group of 5fdC to form stable amide bond. 4-Carboxyphenylboronic acid (4-CPBA) was adopted as crosslinker for 5fdC and amino functionalized CuBi2O4 based on the covalent interaction between 1,3-diol bond on 5fdC and boric acid structure on 4-CPBA, and the covalent interaction between –COOH on 4-CPBA and –NH2 on amino functionalized CuBi2O4. On the basis of the positive synergistic effect of ZnPc and CuBi2O4 on improving the photoelectric performance of WS2, the separation of photo-generated electron-hole pairs in semiconductors were promoted, and the examination range was expanded from 0.1 to 500 nM, and the detection limit was 0.0483 nM (3σ). Based on the unique covalent reaction between –NH2 and –CHO, the PEC biosensor has excellent detection sensitivity, and can even separate 5fdC from 5-methylcytosine deoxyribonucleoside and 5-hydroxymethylcytosine deoxyribonucleoside. The effect of antibiotics and heavy metals on the 5fdC content in wheat tissue genome has also been further investigated using this sensor.

A novel photoelectrochemical (PEC) biosensor was constructed for DNA hydroxymethylation detection based on Bi4NbO8Cl/PTC-NH2 heterojunction and Fe-MIL-88NH2, where Bi4NbO8Cl/PTC-NH2 was employed as photoactive material and Fe-MIL-88NH2 was adopted as artificial hydrogen peroxide mimic enzyme. Based on the structure of hydroxymethylated cytosine in DNA sequence, 5-hydroxymethyl-2’-deoxycytidine (5hmdC) was employed as detected target molecule for the first time using PEC technique. After Bi4NbO8Cl/PTC-NH2 heterojunction was modified on the substrate electrode, thioglycolic acid (TGA) was captured by forming amide bond, where the sulfhydryl group (-SH) of TGA was employed as the specific recognition of 5hmdC. Under M. HhaI catalysis, the −CH2OH of 5hmdC reacted selectively with the –SH. Finally, Fe-MIL-88NH2 was modified on the electrode based on the crosslinker of 4-formylphenylboronic acid (FPBA), where FPBA possessed two active groups of formyl and boronic acid group, reacting with glycosyl of 5hmdC and amino of Fe-MIL-88NH2. Under the catalysis effect of Fe-MIL-88NH2, the insoluble substance was produced on the surface of electrodes, resulting in distinct lessening of PEC response. Under optimal conditions, the photocurrent shows a linear relationship with the logarithm value of 5hmdC concentration from 0.01-100 nM with a low detection limit of 6.48 pM. More importantly, this method can be applied to investigate the influence of exogenous phytohormone on 5hmdC content in the genomic DNA of rice seedling roots and leaves.

An integrated cobalt oxide catalyst supported on silica (Co3O4/SiO2) packed in the lumen of tubular alumina (Al2O3) membrane was designed to realize a Fenton-like oxidation coupling with ultrafiltration water treatment technology to remove persistent and hazardous pollutants. We employed a selection of SiO2 support materials with a range micro/mesostructures to immobilize the Co3O4 catalyst. These were evaluated and screened to achieve the highest pollutant decolorization rate and maximum decolorization efficiency. Then, an integrated catalyst-membrane was developed as proof-of-concept for advanced water treatment. Batch degradation results showed acid orange 7 dye (AO7) was effectively removed using Co3O4 deposited on MCM-41 silica, with 97% decolorization efficiency achieved in 15 mins owing to the large surface area and high porosity of the MCM-41 support. In contrast, humic acid (HA) was relatively difficult to degrade using this catalyst, and was however found to inhibit AO7 degradation. The integrated catalyst-membrane successfully removed both AO7 and HA with only a 10% water flux reduction from 25.0 to 22.5 kg m−2 h−1 bar−1 with excellent co-pollutant removal rate of 99% over 40 h. Furthermore, the integrated catalyst-membrane also removed a range of organic pollutants (neutral red, tetracycline hydrochloride, oxytetracycline) achieving > 90% rejection and 30 kg m−2 h−1 bar−1. These results show that the integrated catalyst-membrane can effectively purify a binary pollutant mixture containing both hazardous dye and natural organic matter and other pharmaceutical chemicals whilst producing process water for recycling and reuse.

BACKGROUND Catalytic distillation (CD) has been received as an inviting green chemical process for numerous catalytic esterification reactions. Rendering novel structured CD packings is particularly desirable but remains challenging. RESULTS We present a microfibrous-structured HZSM-5 solid acid catalyst as CD packings and demonstrate its separation and esterification reaction efficiency for producing ethyl acetate from acetic acid and ethanol. The factorial design based on response surface methodology is employed for fast determination of optimum reaction conditions, which is working effectively and efficiently. Such structured catalyst packings are obtained by direct growth of zeolite onto the θ-ring analogues shaped from a microfibrous-structure consisting of 15 vol% 20 µm stainless-steel-fiber (SS-fiber) and 85 vol% voidage. CONCLUSION The SS-fiber@HZSM-5 packings provide a unique combination of instantaneous distillation and desired catalytic properties with respect to stability, adequate acidic sites and high mass/heat transfer, and therefore work efficiently and effectively. High total (95.9%) and actual (90.9%) yields of ethyl acetate with 89.8% purity are achievable while the high CD efficiency was well-preserved after at least 240 h over 30 consecutive batch runs.

Surfactin is a Bacillus-produced natural lipopeptide, which can overcome the epithelial cell barriers for orally delivering insulin, but its ability to promote uptake of insulin by the intestine need to be further improved for a higher oral bioavailability. Here, we designed and synthesized several surfactin variants to improve its ability for oral delivery of insulin. Firstly, we replaced Glu with Gln in surfactin for decreasing its negative charges, but found this replacement weakened its ability to orally delivery insulin. We further chemically synthesized surfactin variant by replacing its fatty acid chain (C15) with a shortened one (C14), and found this replacement did not influence its ability to orally deliver insulin. Lastly, we replaced its amino acids (Leu) with more hydrophobic ones (Ile), and found the replacement could significantly improve its ability to deliver insulin, with a maximal blood glucose decrease to 27.33% of the initial level and an insulin bioavailability of 18.25%. We also replaced its amino acids of Leu with Val, and Val with Ile, and found this replacement could also significantly improve its ability to deliver insulin with a maximal blood glucose decrease to 18.36% of the initial level and a high insulin bioavailability of 26.32% in diabetic mice. Further analysis by CD, we found the surfactin variants with more hydrophobic amino acid residuals significantly induced insulin from rigid (α-helix) to flexible structure (β-sheet and random coil), that is favorable for insulin to permeate across the intestine epithelial membrane. Collectively, surfactin variants with more hydrophobicity are very potential for delivery of insulin in the everyday control of blood glucose.

Selective adsorption and energy-saving regeneration are two important issues for adsorptive separation. However, it is impossible for traditional adsorbents with changeless pore properties to realize both of them. In this study, a strategy was proposed to design and fabricate a new generation of adsorbents via grafting the thermoresponsive polymers (TPs), namely, poly(N-isopropylacrymide) (PNIPAM), onto the pore surface of mesoporous silica SBA-15. The TPs disperse homogeneously in pore space and act as molecular switches which are reversibly closed or opened with the change of temperature. At the temperature of adsorption below the lower critical solution temperature (LCST), TPs are extended as a result of their extensive hydrogen bonding interactions with water and the molecular switches are closed. It is easier for smaller adsorbates to enter than larger ones, and the selective adsorption can be consequently realized. At the temperature of desorption (above LCST), TPs shrink owing to their hydrogen bon...

Single crystalline Cu 2 SnS 3 nanosheets with exposed (220) planes have been synthesized via a facial solvothermal solution chemical route. The solvent of ethylenediamine hindered the growth along the [110] direction and facilitated the formation of two dimensional nanostructures. Electrochemical performance of Cu 2 SnS 3 electrodes in sodium ion batteries was investigated. Cu 2 SnS 3 electrodes exhibit an initial sodiation capacity of 586 mAh/g and 178 mAh/g after 50 cycles. The electrochemical properties of Cu 2 SnS 3 nanosheets suggest it is a potential anode material for sodium ion batteries.

Cow milk is most widely consumed; however, non-cattle milk has gained increasing interest because of added nutritive values. We compared the health effects of yak, cow, and camel milk in rats. By measuring several plasma immune factors, significantly more interferon-γ was detected in the camel than the yak (P = 0.0020) or cow (P = 0.0062) milk group. Significantly more IgM was detected in the yak milk than the control group (P = 0.0071). The control group had significantly less interleukin 6 than the yak (P = 0.0499) and cow (P = 0.0248) milk groups. The fecal microbiota of the 144 samples comprised mainly of the Firmicutes (76.70 ± 11.03%), Bacteroidetes (15.27 ± 7.79%), Proteobacteria (3.61 ± 4.34%), and Tenericutes (2.61 ± 2.53%) phyla. Multivariate analyses revealed a mild shift in the fecal microbiota along the milk treatment. We further identified the differential microbes across the four groups. At day 14, 22 and 28 differential genera and species were identified (P = 0.0000–0.0462), while 8 and 11 differential genera and species (P = 0.0000–0.0013) were found at day 28. Some short-chain fatty acid and succinate producers increased, while certain health-concerned bacteria (Prevotella copri, Phascolarctobacterium faecium, and Bacteroides uniformis) decreased after 14 days of yak or camel milk treatment. We demonstrated that different animal milk could confer distinctive nutritive value to the host.

A novel solvothermal chemical route has been developed to synthesize Cu–Sb–S compound nanocrystals in a controllable manner. Cu3SbS4 and CuSbS2 nanocrystals can be selectively prepared by modifying the reaction temperature. The temperature dependent release of antimony from potassium antimonyl tartrate trihydrate faciliated the selective synthesis of Cu3SbS4 and CuSbS2. The bandgap is 1.0 eV for Cu3SbS4 nanocrystals and 1.45 eV for CuSbS2 nanocrystals. Semiconductors of Cu–Sb–S compounds with such band gaps are desirable for solar cell applications. The Cu3SbS4 and CuSbS2 nanocrystals both showed obvious photo-electric response, indicating their potential application as an active layer in thin-film solar cells.

Free-standing stainless-steel (SS)-fiber@meso-HZSM-5 core–shell catalysts engineered from micro- to macro-scale were highly efficiently synthesized via cost-effective steam-assisted crystallization (SAC) method. Impact of synthesis conditions on their morphology and textural/acidic properties was investigated by means of XRD, SEM, TEM, solid-state NMR, NH3-TPD, Py-IR and N2 physisorption. Single-run lifetime of such structured catalysts for MTP process was strongly dependent on their preparation conditions but slightly the product distribution. A volcano-like relationship for lifetime was observed against the SAC time, which was correlated well with the crystallization-time-dependent crystallinity, mesoporosity and crystal size. The promising SS-fiber@meso-HZSM-5 was the one obtained after the SAC for 12 h, which delivered a prolonged single-run lifetime of 620 h with a high propylene selectivity of ∼42% at 450 °C using a methanol weight hourly space velocity (WHSV) of 1 h–1, as the result of high crystal...