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Building a reliable relationship between the electronic structure of alloyed metallic catalysts and catalytic performance is important but remains challenging due to the interference from many entangled factors. Herein, a PdBi surface alloy structural model, by tuning the deposition rate of Bi atoms relative to the atomic interdiffusion rate at the interface, realizes a continuous modulation of the electronic structure of Pd. Using advanced X-ray characterization techniques, we provide a precise depiction of the electronic structure of the PdBi surface alloy. As a result, the PdBi catalysts show enhanced propene selectivity compared with the pure Pd catalyst in the selective hydrogenation of propyne. The prevented formation of saturated β-hydrides in the subsurface layers and weakened propene adsorption on the surface contribute to the high selectivity. Our work provides in-depth understanding of the electronic properties of surface alloy structure and underlies the study of the electronic structure-performance relationship in bimetallic catalysts.

To alleviate the energy crisis and global warming, photothermal catalysis is an attractive way to efficiently convert CO2 and renewable H2 into value-added fuels and chemicals. However, the catalytic performance is usually restricted by the trade-off between the dispersity and light absorption property of metal catalysts. Here we demonstrate a simple SiO2-protected metal–organic framework pyrolysis strategy to fabricate a new type of integrated photothermal nanoreactor with a comparatively high metal loading, dispersity, and stability. The core-satellite structured Co@SiO2 exhibits strong sunlight-absorptive ability and excellent catalytic activity in CO2 hydrogenation, which is ascribed to the functional separation of different sizes of Co nanoparticles. Large-sized plasmonic Co nanoparticles are mainly responsible for the light absorption and conversion to heat (nanoheaters), whereas small-sized Co nanoparticles with high intrinsic activities are responsible for the catalysis (nanoreactors). This study provides a new concept for designing efficient photothermal catalytic materials.

A combined structural engineering strategy and thinning strategy were used to optimize nanoarray-based photothermal catalysts, showing a high CO2 conversion rate of 1780 mmol gCo-1 h-1.

Cascade catalysis of reverse water gas shift (RWGS) and well-established CO hydrogenation holds promise for the conversion of greenhouse gas CO2 and renewable H2 into liquid hydrocarbons and methanol under mild conditions. However, it remains a big challenge to develop low-temperature RWGS catalysts with high activity, selectivity, and stability. Here, we report the design of an efficient RWGS catalyst by encapsulating ruthenium clusters with the size of 1 nm inside hollow silica shells. The spatially confined structure prevents the sintering of Ru clusters while the permeable silica layer allows the diffusion of gaseous reactants and products. This catalyst with reduced particle sizes not only inherits the excellent activity of Ru in CO2 hydrogenation reactions but also exhibits nearly 100% CO selectivity and superior stability at 200–500 °C. The ability to selectively produce CO from CO2 at relatively low temperatures paves the way for the production of value-added fuels from CO2 and renewable H2.

Driving metal-cluster-catalyzed high-temperature chemical reactions by sunlight holds promise for the development of negative-carbon-footprint industrial catalysis, which has yet often been hindered by the poor ability of metal clusters to harvest and utilize the full spectrum of solar energy. Here, we report the preparation of Mo

The reverse water–gas shift (RWGS) reaction is a critical step for adjusting the CO/H2 ratio in crude syngas via CO2 hydrogenation in the chemical industry. Generally, the conditioning of syngas co...

The strong metal–support interaction (SMSI) between metals and reducible supports (e.g., CeO2, TiO2, and SnO2), which has been widely investigated, plays a very important role in heterogeneous catalysis. We report the first example of SMSI between palladium (Pd) and gallium oxide (Ga2O3) within a PdGa nanoparticle (denoted as PdxGay NP, where x:y is the atomic ratio of Pd and Ga). The typical features of classic SMSI, such as electron transfer between Ga2O3 and Pd and suppression of H2 and CO adsorption, are successfully observed on PdxGay NPs. Detailed characterizations and control experiments demonstrate that the coexistence of PdGa alloy and Ga2O3 in PdxGay NPs plays a vital role in the formation of SMSI. To systematically study the effects of SMSI on catalytic performance, PdxGay NPs were used as “self-supported catalysts” for propyne semi-hydrogenation (PSH), a critical process for removing trace propyne from propylene in industry. It is shown that optimized Pd0.34Ga1 NPs give a propylene selectivity of 98.2% at a propyne conversion of 96.6% at 30 °C and atmospheric pressure, which is much higher than that of pure Pd NPs and Pd/Ga2O3 catalysts prepared by a conventional wet-impregnation method. The reaction paths of PSH on PdxGay NPs have been further revealed by density functional theory (DFT) calculations. This work may not only deepen the basic understanding of SMSI, but also promote the design and application of heterogeneous catalysts.

The conversion of CO2 into fuels and feedstock chemicals via photothermal catalysis holds promise for efficient solar energy utilization to tackle the global energy shortage and climate change. Despite recent advances, it is of emerging interest to explore promising materials with excellent photothermal properties to boost the performance of photothermal CO2 catalysis. Here, we report the discovery of MXene materials as superior photothermal supports for metal nanoparticles. As a proof-of-concept study, we demonstrate that Nb2C and Ti3C2, two typical MXene materials, can enhance the photothermal effect and thus boost the photothermal catalytic activity of Ni nanoparticles. A record CO2 conversion rate of 8.50 mol·gNi-1·h-1 is achieved for Nb2C-nanosheet-supported Ni nanoparticles under intense illumination. Our study bridges the gap between photothermal MXene materials and photothermal CO2 catalysis toward more efficient solar-to-chemical energy conversions and stimulates the interest in MXene-supported metal nanoparticles for other heterogeneous catalytic reactions, particularly driven by sunlight.

The selective hydrogenation of propyne to propylene has attracted great attention in chemical industry for removing trace amount of propyne for producing polymer-grade propylene. As the state-of-the-art catalyst, Pd suffers from the disadvantage of poor propylene selectivity due to the over-hydrogenation of propylene to propane. We here demonstrate that Pd nanocubes (NCs) coated by zeolitic imidazolate frameworks (i.e., Pd NCs@ZIF-8) can serve as highly active and selective catalysts for propyne selective hydrogenation (PSH). Benefitting from the unique properties and abundant groups of ZIF-8, Pd carbide (Pd-C) is formed on the surface of Pd NCs after thermal treatment, which acts the active sites for PSH to propylene. More importantly, the content of Pd-C can be precisely controlled by altering the calcination temperature without aggregation of Pd NCs and obvious changes in the framework of ZIF-8. The formation of Pd-C on Pd NCs@ZIF-8 can strongly suppress the H2 adsorption, and thus selectively catalyze propyne to propylene. Consequently, the optimized catalyst (i.e., Pd NCs@ZIF-8-100) exhibits a propylene selectivity of 96.4% at a propyne conversion of 93.3% at 35 °C and atmospheric pressure. This work may not only provide an efficient catalyst for PSH, but also shed a new light on the catalytic application of ZIFs.

All-inorganic lead halide perovskite (CsPbX

Single atom catalysts (SACs) have recently attracted great attention in heterogeneous catalysis and have been regarded as ideal models for investigating the strong interaction between metal and support. Despite the huge progress over the past decade, the deep understanding on the structure-performance correlation of SACs at a single atom level still remains to be a great challenge. In this study, we demonstrate that the variation in the coordination number of the Pt single atom can significantly promote the propylene selectivity during propyne semihydrogenation (PSH) for the first time. Specifically, the propylene selectivity greatly increases from 65.4% to 94.1% as the coordination number of Pt-O increases from ∼3.4 to ∼5, whereas the variation in the coordination number of Pt-O slightly influences the turnover frequency values of SACs. We anticipate that the present work may deepen the understanding on the structure-performance of SACs and also promote the fundamental research in single atom catalysis.

Two-dimensional (2D) metal carbides, carbonitrides, and nitrides (MXenes) have recently emerged as promising candidates in catalysis due to their unique properties. In this work, we composited Ti3C...

Background Circular RNAs (circRNAs) have been identified to be involved in onset and progression of multiple malignant tumors. The present study aimed to systematically evaluate the diagnostic values of circRNAs in breast cancer. Methods The PubMed, Web of Science, Embase, CNKI, and Wanfang online databases were searched for the relevant studies before December 31, 2020. Statistical analysis of the diagnostic tests was performed based on STATA 16.0, Meta‐DiSc 1.4, and RevMan 5.3 software. The threshold effect and publication bias were measured by the Spearman correlation and Deeks’ funnel plot asymmetry test, respectively. Results Twenty‐one studies from 13 articles were included in this meta‐analysis. The pooled sensitivity and specificity were 0.77 and 0.71, respectively. The pooled positive likelihood ratio (PLR), negative likelihood ratio (NLR), and overall diagnostic odds ratio (DOR) were 2.6, 0.33, and 8, respectively. Furthermore, the area under the summary receiver operator characteristic curve was 0.80. In addition, down‐regulated circRNAs achieved a diagnostic performance higher than up‐regulated circRNAs, with area under curve (AUC) values of 0.81 and 0.74, respectively. Studies based on tissue samples presented better diagnostic accuracy than those based on plasma samples, with AUC values of 0.80 and 0.67. In addition, two circRNAs, including circ_0001073 and circTADA2A‐E5/E6, showed higher diagnostic values, with AUC value of 0.990 and 0.937, respectively. According to the results of meta‐regression, the case size (p, Thirteen studies comprised of 21 circRNAs were included in this meta‐analysis. Down‐regulated circRNAs achieved a diagnostic performance higher than up‐regulated circRNAs. Tissue‐based circRNA analysis presented better diagnostic accuracy than plasma‐based analysis.

The development of highly selective catalysts has been remarkably relying on the understanding of catalytic active sites. Pd-catalyzed semihydrogenation of propyne has been a focus of research with...

Butadiene (BD) is a critical raw material in chemical industry, which is conventionally produced from naphtha cracking. The fast-growing demand of BD and the limited oil reserve motivate chemists to develop alternative methods for BD production. Shale gas, which mainly consists of light alkanes, has been considered as cheap raw materials to replace oil for BD production via n-butane direct dehydrogenation (n-BDH). However, the quest for highly-efficient catalysts for n-BDH is driven by the current drawback of low BD selectivity. Here, we demonstrate a strategy for boosting the selectivity of BD by suppressing dehydroisomerization, an inevitable step in the conventional n-BDH process which largely reduces the selectivity of BD. Detailed investigations show that the addition of alkali-earth metals (e. g., Mg and Ca) into Pt-Ga2 O3 /S10 catalysts increases Pt dispersity, suppresses coke deposition and dehydroisomerization, and thus leads to the significant increase of BD selectivity. The optimized catalyst displays an initial BD selectivity of 34.7 % at a n-butane conversion of 82.1 % at 625 °C, which outperforms the reported catalysts in literatures. This work not only provides efficient catalysts for BD production via n-BDH, but also promotes the researches on catalyst design in heterogeneous catalysis.

The conversion of CO

Developing efficient Pt-based electrocatalysts for the methanol oxidation reaction (MOR) is of pivotal importance for large-scale application of direct methanol fuel cells (DMFCs), but Pt suffers from severe deactivation brought by the carbonaceous intermediates such as CO. Here, we demonstrate the formation of a bismuth oxyhydroxide (BiOx(OH)y)-Pt inverse interface via electrochemical reconstruction for enhanced methanol oxidation. By combining density functional theory calculations, X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy, and electrochemical characterizations, we reveal that the BiOx(OH)y-Pt inverse interface can induce the electron deficiency of neighboring Pt; this would result in weakened CO adsorption and strengthened OH adsorption, thereby facilitating the removal of the poisonous intermediates and ensuring the high activity and good stability of Pt2Bi sample. This work provides a comprehensive understanding of the inverse interface structure and deep insight into the active sites for MOR, offering great opportunities for rational fabrication of efficient electrocatalysts for DMFCs.

In this work, transgenic lines of suspension cultured cells of Vitis vinifera cv. Monastrell containing the plasmid pMOG800-sts have been obtained. The cell growth of these transgenic cell lines decreased slightly as compared to non-transgenic suspension cultured cells, while cell viability was not affected. In addition, the elicitation with cyclodextrins and methyl jasmonate enhanced the production of trans-resveratrol, observing the highest levels of this compound in sts-expressing transgenic Vitis suspension cultured cells with the sts expression cassette in the forwards orientation. Moreover, the forwards 2 (F2) transgenic cell line produced the greater levels of trans-resveratrol in comparison with the non-transgenic cell line. In fact, when suspension cultured cells were treated with both elicitors, the accumulation of trans-resveratrol outside the cells in the F2 transgenic suspension cultured cells increased twice (1458 mg.L-1) as compared to non-transgenic cell lines (724 mg.L-1). In both cases, the levels of trans-resveratrol detected in the treatment with cyclodextrins and methyl jasmonate were greater than the sum of the individual treatments, and therefore we observed a synergistic effect in the presence of both elicitors. Moreover, the expression profile of sts gene in transgenic V. vinifera cell lines was similar to the expression profile detected for the endogenous sts gene in non-transgenic V. vinifera cell lines, being the expression levels greater in the treatment with methyl jasmonate and cyclodextrins, which was related to the high levels of trans-resveratrol found in the presence of both elicitors.

Although some works have explored the transformation of differentiated, embryogenic suspension-cultured cells (SCC) to produce transgenic grapevine plants, to our knowledge this is one of the first reports on the efficient transformation of dedifferentiated Vitis vinifera cv Monastrell SCC. This protocol has been developed using the sonication-assisted Agrobacterium-mediated transformation (SAAT) method. A construct harboring the selectable nptII and the eyfp/IV2 marker genes was used in the study and transformation efficiencies reached over 50 independent transformed SCC per gram of infected cells. Best results were obtained when cells were infected at the exponential phase. A high density plating (500 mg/dish) gave significantly better results. As selective agent, kanamycin was inefficient for the selection of Monastrell transformed SCC since wild type cells were almost insensitive to this antibiotic whereas application of paromomycin resulted in very effective selection. Selected eyfp-expressing microcalli were grown until enough tissue was available to scale up a new transgenic SCC. These transgenic SCC lines were evaluated molecularly and phenotypically demonstrating the presence and integration of both transgenes, the absence of Agrobacterium contamination and the ability of the transformed SCC to grow in highly selective liquid medium. The methodology described here opens the possibility of improving the production of valuable metabolites. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:725-734, 2016.