Application of transition metal phosphide (TMP) catalysts for full water splitting has great potential to help relieve the energy crisis. Various methods have been investigated to obtain high catalytic activity, but the use of electronic structure regulation by incorporation of different elements is of particular simplicity and significance for development of a universal TMP synthesis method. We herein describe a novel approach for fabricating a series of TMPs by pyrolyzing phytic acid (PA) cross-linked metal complexes. The introduction of oxygen atoms into TMPs not only enhanced their intrinsic electrical conductivity, facilitating electron transfer, but activated active sites via elongating the M-P bond, favoring the hydrogen evolution reaction (HER) or oxygen evolution reaction (OER). MoP exhibited relative low HER overpotentials of 118 mV and 93 mV while supporting a current density of 20 mA·cm in 0.5 M HSO and 1 M KOH electrolytes, respectively. When CoP was applied as a catalyst for OER, only 280 mV overpotential was required to reach current density of 10 mA·cm. Additionally, PA-containing precursors enabled intimate embedding of TMPs onto a flexible substrate surface (carbon cloth), so that electron injection from substrate and transport to the active sites was facilitated. Remarkably, an alkaline electrolyzer was able to achieve a current density of 40 mA·cm at the low voltage of 1.6 V, demonstrating its potential for practical overall water splitting without the use of noble metals.
The layered molybdenum chalcogenide MoS 2 has attracted wide attention due to its potential electrochemical applications. Based on its unique physical and chemical properties, numerous advances have shown that nanostructured MoS 2 , with the advantages of low cost and outstanding properties, is a promising candidate for environmentally benign energy conversion and storage (ECS) devices.Nowadays, in order to lessen the reliance on fossil fuels, the production of hydrogen from water splitting has become an important issue. Hence, developing catalysts composed of earth-abundant elements that possess activities comparable to those of noble metals is of great urgency. According to DFT calculations in terms of HER free-energy diagrams, MoS 2 could be used as an effective substitute for noble metals. Meanwhile, MoS 2 with various structures has also been applied in the field of energy storage, including batteries and supercapacitors. Additionally, due to their layer-dependent electrical properties, MoS 2 -based electrochemical devices have been applied as sensors for a variety of chemicals.In this review, we summarize recent advances in the development of MoS 2 with high-performance in various electrochemical domains, and recent progress in discovering the mechanisms underlying the enhanced activity. Moreover, we summarize the critical obstacles facing MoS 2 , and discuss strategies for further improving its activity. Lastly, we offer some suggestions on the pathways toward achieving high performance competitive with noble metal counterparts, and perspectives on practical applications of MoS 2 in the future. Broader contextThe development of inexhaustible and clean energy technologies has far-reaching benefits for our society. Owing to its high anisotropy and unique crystal structure, the attractive properties of 2D molybdenum disulfide (MoS 2 ) can be utilized in a variety of energy conversion and storage (ECS) applications. Therefore, understanding how these properties can be tuned and the tunable properties can be utilized becomes increasingly important. In this review, we first summarize recent synthetic strategies toward preparation of MoS 2 with different structures, and its role in several important renewable energy technologies. We then discuss the relationship between the tuned properties and the performance of MoS 2 in different applications, emerging trends during their development, and challenges facing them, offering our perspectives on how to effectively advance the development of MoS 2 -based devices.
Adsorbent OxidationArsenite Removal a b s t r a c t Arsenite (As(III)) is more toxic and more difficult to remove from water than arsenate (As(V)).As there is no simple treatment for the efficient removal of As(III), an oxidation step is always necessary to achieve higher removal. However, this leads to a complicated operation and is not cost-effective. To overcome these disadvantage, a novel Fe-Mn binary oxide material which combined the oxidation property of manganese dioxide and the high adsorption features to As(V) of iron oxides, were developed from low cost materials using a simultaneous oxidation and coprecipitation method. The adsorbent was characterized by BET surface areas measurement, powder XRD, SEM, and XPS. The results showed that prepared Fe-Mn binary oxide with a high surface area ð265 m 2 g À1 Þ was amorphous. Iron and manganese existed mainly in the oxidation state þIII and IV, respectively. Laboratory experiments were carried out to investigate adsorption kinetics, adsorption capacity of the adsorbent and the effect of solution pH values on arsenic removal. Batch experimental results showed that the adsorbent could completely oxidize As(III) to As(V) and was effective for both As(V) and As(III) removal, particularly the As(III). The maximal adsorption capacities of As(V) and As(III) were 0:93 mmol g À1 and 1:77 mmol g À1 , respectively. The results compare favorably with those obtained using other adsorbent. The effects of anions such as SO 2À 4 , PO 3À 4 , SiO and humic acid (HA), which possibly exist in natural water, on As(III) removal were also investigated. The results indicated that phosphate was the greatest competitor with arsenic for adsorptive sites on the adsorbent. The presence of sulfate and HA had no significant effect on arsenic removal. The high uptake capability of the Fe-Mn binary oxide makes it potentially attractive adsorbent for the removal of As(III) from aqueous solution.
Low‐cost and resourceful transition metal phosphides (TMPs) have gradually received wide acceptance in the energy industry through exhibiting comparable catalytic activity and long‐term stability to traditional catalysts (e.g., Pt/C, LiCoO2, LiFePO4, etc.). With the emergence of the research hotspot of TMPs, probing their mechanism of catalytic energy conversion and storage inspired by the superb structure of metal‐phosphorus chelate is of great significance. To this end, recent developments in TMPs with various crystal structures and morphologies have attracted much attention. The design of TMPs ranging from the choice of different transition metals to phosphorus sources has been intensively explored. This research has indicated that multidimensional morphologies of TMPs prominently enrich the patterns of charge storage and electron transportation, and ultra‐nanoscaled TMPs obtained by multiple tools and techniques might challenge the threshold of electrocatalytic reactions. Here, recent developments in synthetic strategies of TMPs from different precursors are classified. The underlying mechanism between the structural and crystallographic characteristics and the tuned properties of TMPs in energy applications is also presented. Additionally, the key trends in structure and morphology characterization of TMPs are highlighted. Future perspectives on the challenges and opportunities facing TMPs catalysts are thereby proposed.
A novel Fe-Mn binary oxide adsorbent was developed for effective As(III) removal, which is more difficult to remove from drinking water and much more toxic to humans than As(V). The synthetic adsorbent showed a significantly higher As(III) uptake than As(V). The mechanism study is therefore necessary for interpreting such result and understanding the As(III) removal process. A control experiment was conducted to investigate the effect of Na2SO3-treatment on arsenic removal, which can provide useful information on As(III) removal mechanism. The adsorbent was first treated by Na2SO3, which can lower its oxidizing capacity by reductive dissolution of the Mn oxide and then reacted with As(V) or As(III). The results showed that the As(V) uptake was enhanced while the As(III) removal was inhibited after the pretreatment, indicating the important role of manganese dioxide during the As(III) removal. FTIR along with XPS was used to analyze the surface change of the original Fe-Mn adsorbent and the pretreated adsorbent before and after reaction with As(V) or As(III). Change in characteristic surface hydroxyl groups (Fe-OH, 1130, 1048, and 973 cm(-1)) was observed by the FTIR. The determination of arsenic oxidation state on the solid surface after reaction with As(III) revealed that the manganese dioxide instead of the iron oxide oxidized As(III) to As(V). The iron oxide was dominant for adsorbing the formed As(V). An oxidation and sorption mechanism for As(III) removal was developed. The relatively higher As(III) uptake may be attributed to the formation of fresh adsorption sites at the solid surface during As(III) oxidation.
DNA polymorphism is the basis to develop molecular markers that are widely used in genetic mapping today. A genome-wide rice (Oryza sativa) DNA polymorphism database has been constructed in this work using the genomes of Nipponbare, a cultivar of japonica, and 93-11, a cultivar of indica. This database contains 1,703,176 single nucleotide polymorphisms (SNPs) and 479,406 Insertion/Deletions (InDels), approximately one SNP every 268 bp and one InDel every 953 bp in rice genome. Both SNPs and InDels in the database were experimentally validated. Of 109 randomly selected SNPs, 107 SNPs (98.2%) are accurate. PCR analysis indicated that 90% (97 of 108) of InDels in the database could be used as molecular markers, and 68% to 89% of the 97 InDel markers have polymorphisms between other indica cultivars (Guang-lu-ai 4 and Long-te-pu B) and japonica cultivars (Zhong-hua 11 and 9522). This suggests that this database can be used not only for Nipponbare and 93-11, but also for other japonica and indica cultivars. While validating InDel polymorphisms in the database, a set of InDel markers with each chromosome 3 to 5 marker was developed. These markers are inexpensive and easy to use, and can be used for any combination of japonica and indica cultivars used in this work. This rice DNA polymorphism database will be a valuable resource and important tool for map-based cloning of rice gene, as well as in other various research on rice (http://shenghuan.shnu.edu.cn/ricemarker).
Twist is a critical epithelial-mesenchymal transition (EMT)-inducing transcription factor that increases expression of vimentin. How Twist1 regulates this expression remains unclear. Here, we report that Twist1 regulates Cullin2 (Cul2) circular RNA to increase expression of vimentin in EMT. Twist1 bound the Cul2 promoter to activate its transcription and to selectively promote expression of Cul2 circular RNA (circ-10720), but not mRNA. circ-10720 positively correlated with Twist1, tumor malignance, and poor prognosis in hepatocellular carcinoma (HCC). Twist1 promoted vimentin expression by increasing levels of circ-10720, which can absorb miRNAs that target vimentin. circ-10720 knockdown counteracted the tumor-promoting activity of Twist1 and in patient-derived xenograft and diethylnitrosamine-induced TetOn-Twist1 transgenic mouse HCC models. These data unveil a mechanism by which Twist1 regulates vimentin during EMT. They also provide potential therapeutic targets for HCC treatment and provide new insight for circular RNA (circRNA)-based diagnostic and therapeutic strategies. A circRNA-based mechanism drives Twist1-mediated regulation of vimentin during EMT and provides potential therapeutic targets for treatment of HCC. http://cancerres.aacrjournals.org/content/canres/78/15/4150/F1.large.jpg .
The growing world population and shrinkage of arable land demand yield improvement of rice, one of the most important staple crops. To elucidate the genetic basis of yield and uncover its associated loci in rice, we resequenced the core recombinant inbred lines of Liang-YouPei-Jiu, the widely cultivated super hybrid rice, and constructed a high-resolution linkage map. We detected 43 yield-associated quantitative trait loci, of which 20 are unique. Based on the high-density physical map, the genome sequences of paternal variety 93-11 and maternal cultivar PA64s of Liang-You-Pei-Jiu were significantly improved. The large recombinant inbred line population combined with plentiful high-quality single nucleotide polymorphisms and insertions/deletions between parental genomes allowed us to fine-map two quantitative trait loci, qSN8 and qSPB1, and to identify days to heading8 and lax panicle1 as candidate genes, respectively. The quantitative trait locus qSN8 was further confirmed to be days to heading8 by a complementation test. Our study provided an ideal platform for molecular breeding by targeting and dissecting yieldassociated loci in rice.Oryza sativa | QTL dissection | genome sequence update R ice is one of the most important staple crops in the world and serves as a model for monocots (1). Currently, rice breeding faces the challenge of overcoming the yield plateau. All important agronomic traits would ultimately need to consider their impacts on the yield, which is linked to various growth and developmental components, such as tiller number, seed number and set, and grain weight, to name a few. A number of quantitative trait loci (QTLs) have been reported to control these components, including those revealed by map-based cloning studies, such as IPA1/WFP for tiller and spikelet numbers (2, 3); days to heading8 (DTH8)/Ghd8 and Ghd7 for heading date, plant height, and spikelet number (4, 5); Gn1 for spikelet number (6); GIF1 for seed set (7); and grain size3 (GS3) and GW5 for grain size and weight (8, 9). Although a series of QTLs for yield components have been cloned, elucidation of the genetic mechanisms underlying the inheritance of superior yield in super hybrid rice still has a long way to go.Hybrid rice has a notable contribution to yield improvement. Various commercialized hybrids are derived by crossing different varieties within or between two subspecies, Oryza sativa ssp. indica and ssp. japonica (10, 11). As a pioneer super hybrid rice, Liang-You-Pei-Jiu (LYP9) realized the target of 10.5 tons/ha in 2000 (12). LYP9 was developed by a cross of the paternal 93-11, an indica variety widely grown in China (13), and the maternal PA64s cultivar with a mixed genetic background of indica and javanica. To date, it has been widely cultivated for commercial production in China. Such a feature was thought to make LYP9 recombinant inbred lines (RILs) ideal materials for exploring molecular mechanisms underlying rice yield.Here, we constructed a high-density linkage map by resequencing the parents of LYP9 and 132 c...
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