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1.
Small ; 17(8): e2006834, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33522142

RESUMO

Clear recognition and rational construction of suitable active center for specific reaction is always of great significance in designing highly efficient catalysts. Herein, a dual-active-site copper catalyst (DAS-Cu) containing both CuN3 and CuN4 sites is reported. Such catalysts show extremely high catalytic performance (yield: up to 97%) toward oxyphosphorylation of alkenes, while catalysts with single active site (CuN3 or CuN4 ) are chemically inert in this reaction. Combined with theoretical and experimental results, the different roles of two different Cu active sites in this reaction are further identified. CuN3 site captures the oxygen and trigger further oxidizing process, while CuN4 site provides moderate adsorption sites for the protection of phosphonyl radicals. This work deeply discloses the significant cooperated role with two single-atomic sites in one catalytic active center and brings up a valuable clue for the rational design of better-performing heterogeneous catalyst.

2.
Chem Commun (Camb) ; 57(17): 2164-2167, 2021 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-33524088

RESUMO

We successfully fabricate a novel concave nanostructure that is composed of atomically dispersed Ru atoms in Pt3Sn nanoconcaves (Ru-Pt3Sn NCs), which shows enhanced performance in methanol electroxidation compared to commercial Pt/C. This could be ascribed to the stable intermetallic structure and active surface structure, as well as the synergy among Pt, Sn and Ru.

3.
Environ Technol ; : 1-12, 2021 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-33576725

RESUMO

The current environmental problems urgently require researchers to seek an environmentally friendly, effective and easy to operate sewage treatment method. Graphite carbon nitride (g-C3N4), which has the advantages of simple preparation, safety, non-toxicity and chemical resistance, was expected to become a photocatalyst for solving environmental pollution. However, the performances of g-C3N4 still have some limitations that the electron hole recombination is fast and the powder is not easy to recover. In this study, zinc-doped graphite carbon nitride photocatalyst (Zn-g-C3N4) was mixed with polyacrylonitrile (PAN) to produce photocatalyst fibres by electrospinning. It not only solves the problem that the powder catalyst is difficult to recycle, but also effectively inhibits the recombination of photoelectron-hole pairs. Zn-g-C3N4/PAN has good photocatalytic activity for the simultaneous reduction of hexavalent chromium and degradation of pharmaceuticals. When organic pollutants are present, the reduction efficiency of hexavalent chromium was improved without affecting its own removal efficiency. The potential application value of Zn-g-C3N4/PAN catalytic fibre was further explored by simulating the complex actual water environment. The composite fibre can be easily reused and keep its superior photocatalytic performance. The mechanism of pharmaceuticals degradation was proposed, in which ∙O2- is the most important active species, which leads to the oxidation of pharmaceuticals. Besides, the photoelectrons generated by the catalyst can reduce the toxic hexavalent chromium. The efficiency of Zn-g-C3N4 to remove pollutants is improved by PAN fibre as a carrier, which not only solves the problem of difficult recovery of powder catalysts, but also provides more active sites.

4.
Chem Commun (Camb) ; 2021 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-33616591

RESUMO

Heterogeneous catalysts, as crucial industrial commodities, play an important role in industrial production, especially in energy catalysis. Traditional noble metal catalysts cannot meet the increasing demand. Therefore, the exploration of cost-effective catalysts with high activity and selectivity is important to promote chemical production. Single-atom alloy (SAA) catalysts reduce the use of precious metals compared with traditional catalysts. The unique structure of SAAs, extremely high atom utilization and high catalytic selectivity give them a prominent position in heterogeneous catalysis. SAAs are widely used in selective hydrogenation/dehydrogenation, carbon dioxide reduction reaction (CO2RR), hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and nitric oxide reduction reaction (NORR). Here, the applications and research progress of copper-based single-atom alloys in the various catalytic reactions mentioned above are mainly introduced, and the factors (such as synthesis method, composition content, etc.) affecting the catalytic performance are analyzed using a combination of various characterization and testing methods.

5.
Artigo em Inglês | MEDLINE | ID: mdl-33412851

RESUMO

Single-atom catalysts (SACs) have great potential to revolutionize heterogeneous catalysis, enabling fast and direct construction of desired products. Given their notable promise, a general and scalable strategy to access these catalyst systems is highly desirable. Herein, we describe a straightforward and efficient thermal atomization strategy to create atomically dispersed palladium atoms anchored on a nitrogen-doped carbon shell over an SBA-15 support. Their presence was confirmed by spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurement. The nitrogen-containing carbon shells provide atomic diffusion sites for anchoring palladium atoms emitted from palladium nanoparticles. This catalyst showed exceptional efficiency in selective hydrogenation of phenylacetylene and other types of alkynes. Importantly, it showed excellent stability, recyclability, and sintering-resistant ability. This approach can be scaled up with comparable catalytic activity. We anticipate that this work may lay the foundation for rapid access to high-quality SACs that are amenable to large-scale production for industrial applications.

6.
Nat Commun ; 12(1): 303, 2021 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-33436610

RESUMO

The construction of enzyme-inspired artificial catalysts with enzyme-like active sites and microenvironment remains a great challenge. Herein, we report a single-atomic-site Co catalyst supported by carbon doped boron nitride (BCN) with locally polarized B-N bonds (Co SAs/BCN) to simulate the reductive dehalogenases. Density functional theory analysis suggests that the BCN supports, featured with ionic characteristics, provide additional electric field effect compared with graphitic carbon or N-doped carbon (CN), which could facilitate the adsorption of polarized organochlorides. Consistent with the theoretical results, the Co SAs/BCN catalyst delivers a high activity with nearly complete dechlorination (~98%) at a potential of -0.9 V versus Ag/AgCl for chloramphenicol (CAP), showing that the rate constant (k) contributed by unit mass of metal (k/ratio) is 4 and 19 times more active than those of the Co SAs/CN and state-of-the-art Pd/C catalyst, respectively. We show that Co single atoms coupled with BCN host exhibit high stability and selectivity in CAP dechlorination and suppress the competing hydrogen evolution reaction, endowing the Co SAs/BCN as a candidate for sustainable conversion of organic chloride.

7.
Chem Commun (Camb) ; 57(15): 1895-1898, 2021 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-33491703

RESUMO

Herein, we report a general strategy based on host-guest interactions to fabricate atomically dispersed biomimetic catalysts, which were evaluated by diboration of phenylacetylene. The structure and function of these mimics are quite similar to those of enzymes, namely, the atomically dispersed metal serves as an active site, the external macromolecular structure plays a role as an enzyme catalytic pocket to stabilize the reaction intermediates and the interactions between the intermediates and functional groups near to the active site can reduce the reaction activation energy.

8.
Chemosphere ; 273: 129545, 2021 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-33497981

RESUMO

The overuse of antimicrobials has resulted in serious damage to the ecosystem and human health. Therefore, the development of an efficient, stable, and reusable catalyst to eliminate antimicrobials under mild conditions is highly desired. Drawing inspiration from the metabolism of drugs by the enzymes in the human body, such as heme catalase, we developed a simulated enzyme catalyst, perchloride iron phthalocyanine (FePcCl16), immobilized on pyridine-modified multiwalled carbon nanotubes (FePcCl16-Py-MWCNTs). In the catalyst, FePcCl16 worked as the active site, and the axial fifth ligand, 4-aminopyridine, was introduced to cleave H2O2 heterolytically. Inspired by the reaction mechanism of heme catalase and H2O2, the catalytic system was designed based on FePcCl16-Py-MWCNTs for oxidizing 4-chloro-3,5-dimethylphenol (PCMX) by H2O2 activation. The results showed that the catalytic activity of the system was significantly increased under simulated solar light irradiation, which can promote electron transfer for heterolytic cleavage of H2O2. The enzyme-like catalyst achieved much higher catalytic activity than the Fenton reaction when the pH was close to neutral. It turned out that the main active species was high-valent iron-oxo (Fe(Ⅳ) = O) rather than hydroxyl radial (•OH) or superoxide radical (•O2-), different from most mechanisms. Ultraperformance liquid chromatography-high-definition mass spectrometry showed that the substrate was degraded to small molecule acids by Fe(Ⅳ) = O active species and further mineralization indicated by total organic carbon. The catalytic system exhibited highly efficient, stable, recyclable catalytic performance under mild conditions and did not cause secondary pollution to the environment. This study of a simulated enzyme catalytic system offers important insight into sewage treatment.

9.
J Environ Sci (China) ; 99: 260-266, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33183703

RESUMO

Metal phthalocyanine has been extensively studied as a catalyst for degradation of carbamazepine (CBZ). However, metal phthalocyanine tends to undergo their own dimerization or polymerization, thereby reducing their activity points and affecting their catalytic properties. In this study, a catalytic system consisting of O-bridged iron perfluorophthalocyanine dimers (FePcF16-O-FePcF16), multi-walled carbon nanotubes (MWCNTs) and H2O2 was proposed. The results showed MWCNTs loaded with FePcF16-O-FePcF16 can achieve excellent degradation of CBZ with smaller dosages of FePcF16-O-FePcF16 and H2O2, and milder reaction temperatures. In addition, the results of experiments revealed the reaction mechanism of non-hydroxyl radicals. The highly oxidized high-valent iron-oxo (Fe(IV)=O) species was the main reactive species in the FePcF16-O-FePcF16/MWCNTs/H2O2 system. It is noteworthy that MWCNTs can improve the dispersion of FePcF16-O-FePcF16, contributing to the production of highly oxidized Fe(IV)=O. Then, the pathway of CBZ oxidative degradation was speculated, and the study results also provide new ideas for metal phthalocyanine-loaded carbon materials to degrade emerging pollutants.


Assuntos
Ferro , Nanotubos de Carbono , Carbamazepina , Peróxido de Hidrogênio , Oxirredução
10.
Artigo em Inglês | MEDLINE | ID: mdl-33296190

RESUMO

Single-atom catalysis represents a new frontier that integrates the merits of homogeneous and heterogeneous catalysis to afford exceptional atom efficiency, activity, and selectivity for a range of catalytic systems. Herein we describe a simple defect engineering strategy to construct an atomically dispersed palladium catalyst (Pdδ+, 0 < δ < 2) by anchoring the palladium atoms on oxygen vacancies created in CeO2 nanorods. This was confirmed by spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurement. The as-prepared catalyst showed exceptional catalytic performance in the hydrogenation of styrene (99% conversion, TOF of 2410 h-1), cinnamaldehyde (99% conversion, 99% selectivity, TOF of 968 h-1), as well as oxidation of triethoxysilane (99% conversion, 79 selectivity, TOF of 10 000 h-1). This single-atom palladium catalyst can be reused at least five times with negligible activity decay. The palladium atoms retained their dispersion on the support at the atomic level after thermal stability testing in Ar at 773 K. Most importantly, this synthetic method can be scaled up while maintaining catalytic performance. We anticipate that this method will expedite access to single-atom catalysts with high activity and excellent resistance to sintering, significantly impacting the performance of this class of catalysts.

11.
Int J Oncol ; 2020 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-33367927

RESUMO

Mammalian target of rapamycin (mTOR) serves an important role in regulating various biological processes, including cell proliferation, metabolism, apoptosis and autophagy. Among these processes, energy metabolism is the dominant process. The metabolism of not only amino acids, fatty acids and lipids, but also that of nucleotides and glucose has been indicated to be regulated by mTOR. Aerobic glycolysis, which is a specific form of glucose metabolism, is prevalent in carcinomas, and it has been considered to be a potential target for cancer therapy. In reviewing the complexity of the mTOR pathway, it is important to elucidate the central role and detailed pathway via which mTOR regulates glycolysis. In the present study, the complex mechanisms via which mTOR regulates aerobic glycolysis were comprehensively reviewed to highlight the potential of drug development via targeting the molecules associated with mTOR and glycolysis and to further provide strategies for the clinical treatment of cancer.

12.
Artigo em Inglês | MEDLINE | ID: mdl-33211492

RESUMO

Heterogeneous catalysts with atomically precise metal sites have enabled unique insight into structure-property relationships in materials science. Herein, we report the construction and selective hydrogenation performance of a single-atom palladium catalyst by confining the palladium atoms into the six-fold N-coordinating cavities of graphitic carbon nitride (g-C3N4) through a facile spatial confinement-reduction approach under mild reducing conditions. Spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements confirm the presence of atomically dispersed palladium atoms stabilized by the g-C3N4 support. Its exceptional catalytic activity was demonstrated by the hydrogenation of styrene (98% conversion, 1.5 h) and furfural (conversion of 64% and selectivity of 99%, 4 h) and hydrodechlorination of 4-chlorophenol (99% conversion and 99% selectivity, 10 min). This palladium catalyst can be reused at least five times with negligible deterioration of its activity. Importantly, the palladium atoms retained their atomic dispersion following the thermal treatment. Moreover, this synthetic method can be scaled up while retaining similar catalytic activity. Fundamental insights are provided to elucidate how the material's structure significantly impacts the catalytic performance at the atomic scale.

13.
Artigo em Inglês | MEDLINE | ID: mdl-33124719

RESUMO

Demonstrated here is the correlation between atomic configuration induced electronic density of single-atom Co active sites and oxygen reduction reaction (ORR) performance by combining density-functional theory (DFT) calculations and electrochemical analysis. Guided by DFT calculations, a MOF-derived Co single-atom catalyst with the optimal Co1 -N3 PS active moiety incorporated in a hollow carbon polyhedron (Co1 -N3 PS/HC) was designed and synthesized. Co1 -N3 PS/HC exhibits outstanding alkaline ORR activity with a half-wave potential of 0.920 V and superior ORR kinetics with record-level kinetic current density and an ultralow Tafel slope of 31 mV dec-1 , exceeding that of Pt/C and almost all non-precious ORR electrocatalysts. In acidic media the ORR kinetics of Co1 -N3 PS/HC still surpasses that of Pt/C. This work offers atomic-level insight into the relationship between electronic density of the active site and catalytic properties, promoting rational design of efficient catalysts.

14.
J Am Chem Soc ; 142(39): 16861-16867, 2020 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-32924470

RESUMO

Electrocatalysis of the four-electron oxygen reduction reaction (ORR) provides a promising approach for energy conversion, storage, and oxygen monitoring. However, it is always accompanied by the reduction of hydrogen peroxide (H2O2) on most employed catalysts, which brings down the electrocatalytic selectivity. Here, we report a single-atom Co-N4 electrocatalyst for the four-electron ORR at an onset potential of 0.68 V (vs RHE) in neutral media while with high H2O2 tolerance, outperforming commercial Pt electrocatalysts. Electrochemical kinetic analysis confirms that the Co-N4 catalytic sites dominantly promote the direct four-electron pathway of the ORR rather than the two sequential two-electron reduction pathways with H2O2 as the intermediate. Density functional theory calculations reveal that H2O2 reduction is hampered by the weak adsorption of H2O2 on the porphyrin-like Co centers. This endows the electrocatalyst with improved resistance to current interference from H2O2, enabling highly selective O2 sensing as validated by the reliable sensing performance in vivo. Our study demonstrates the intriguing advantage of single-atom catalysts with high capacity for tailoring metal-adsorbate interactions, broadening their applications in environmental and life monitoring.

15.
Theranostics ; 10(23): 10665-10679, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32929373

RESUMO

Background: Gut microbiota, which plays a crucial role in inflammatory bowel diseases (IBD), might have therapeutic benefits for ulcerative colitis or Crohn's disease. Targeting gut microbiota represents a new treatment strategy for IBD patients. Rhein is one of the main components of rhubarb and exhibits poor oral bioavailability but still exerts anti-inflammatory effects in some diseases. Therefore, we investigated the effect of rhein on colitis and studied its possible mechanisms. Methods: The chronic mouse colitis model was induced by four rounds of 2% dextran sulfate sodium (DSS) treatment. The mice were treated with 50 mg/kg and 100 mg/kg rhein daily, body weight, colon length, histological score, inflammatory cytokines in serum or intestine, and fecal lipocalin 2 concentration were determined. Th17 cell, Th1 cell and Th2 cell infiltration in the mesenteric lymph node were analyzed by flow cytometry. Metabolic profiles were collected by non-targeted metabolomics and key metabolic pathways were identified using MetaboAnalyst 4.0. We also assessed intestinal barrier permeability and performed 16s rDNA sequencing. Lactobacillus sp. was cultured, and fecal microbiota transplantation (FMT) was employed to evaluate the contribution of gut microbiota. Results: Rhein could significantly alleviate DSS-induced chronic colitis. Uric acid was identified as a crucial modulator of colitis and rhein treatment led to decreased uric acid levels. We determined that rhein changed purine metabolism indirectly, while the probiotic Lactobacillus was involved in the regulation of host metabolism. Uric acid resulted in a worsened intestinal barrier, which could be rescued by rhein. We further confirmed that rhein-treated gut microbiota was sufficient to relieve DSS-induced colitis by FMT. Conclusion: We showed that rhein could modulate gut microbiota, which indirectly changed purine metabolism in the intestine and subsequently alleviated colitis. Our study has identified a new approach to the clinical treatment of colitis.

16.
Angew Chem Int Ed Engl ; 59(50): 22465-22469, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-32876989

RESUMO

Main-group element indium (In) is a promising electrocatalyst which triggers CO2 reduction to formate, while the high overpotential and low Faradaic efficiency (FE) hinder its practical application. Herein, we rationally design a new In single-atom catalyst containing exclusive isolated Inδ+ -N4 atomic interface sites for CO2 electroreduction to formate with high efficiency. This catalyst exhibits an extremely large turnover frequency (TOF) up to 12500 h-1 at -0.95 V versus the reversible hydrogen electrode (RHE), with a FE for formate of 96 % and current density of 8.87 mA cm-2 at low potential of -0.65 V versus RHE. Our findings present a feasible strategy for the accurate regulation of main-group indium catalysts for CO2 reduction at atomic scale.

17.
Angew Chem Int Ed Engl ; 59(46): 20465-20469, 2020 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-32715586

RESUMO

Herein, we report a negative pressure pyrolysis to access dense single metal sites (Co, Fe, Ni etc.) with high accessibility dispersed on three-dimensional (3D) graphene frameworks (GFs), during which the differential pressure between inside and outside of metal-organic frameworks (MOFs) promotes the cleavage of the derived carbon layers and gradual expansion of mesopores. In situ transmission electron microscopy and Brunauer-Emmett-Teller tests reveal that the formed 3D GFs possess an enhanced mesoporosity and external surface area, which greatly favor the mass transport and utilization of metal sites. This contributes to an excellent oxygen reduction reaction (ORR) activity (half-wave potential of 0.901 V vs. RHE). Theoretical calculations verify that selective carbon cleavage near Co centers can efficiently lower the overall ORR theoretical overpotential in comparison with intact atomic configuration.

18.
J Ginseng Res ; 44(4): 580-592, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32617038

RESUMO

Background: Radix et Rhizoma Ginseng (thereafter called ginseng) has been used as a medicinal herb for thousands of years to maintain people's physical vitality and is also a non-organ-specific cancer preventive and therapeutic traditional medicine in several epidemiologic and preclinical studies. Owing to few toxic side effects and strong enhancement on body immunity, ginseng has admirable application potential and value in cancer chemoprevention. The study aims at investigating the chemopreventive effects of ginseng on cutaneous carcinoma and the underlying mechanisms. Methods: The mouse skin cancer model was induced by 7,12-dimethylbenz[a]anthracene/12-O-tetradecanoylphorbol-13-acetate. Ultraperformance liquid chromatography/mass spectrometry was used for identifying various ginsenosides, the main active ingredients of ginseng. Comprehensive approaches (including network pharmacology, bioinformatics, and experimental verification) were used to explore the potential targets of ginseng. Results: Ginseng treatment inhibited cutaneous carcinoma in terms of initiation and promotion. The content of Rb1, Rb2, Rc, and Rd ginsenosides was the highest in both mouse blood and skin tissues. Ginseng and its active components well maintained the redox homeostasis and modulated the immune response in the model. Specifically, ginseng treatment inhibited the initiation of skin cancer by enhancing T-cell-mediated immune response through upregulating HSP27 expression and inhibited the promotion of skin cancer by maintaining cellular redox homeostasis through promoting nuclear translocation of Nrf2. Conclusion: According to the study results, ginseng can be potentially used for cutaneous carcinoma as a chemopreventive agent by enhancing cell-mediated immunity and maintaining redox homeostasis with multiple components, targets, and links.

19.
Adv Mater ; 32(34): e2000896, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32686283

RESUMO

Single-atomic-site (SAS) catalysts, a new frontier of catalysts, always show extremely high atom efficiency and unexpected catalytic properties. Herein, a pyrolyzing coordinated polymer (PCP) strategy is developed, which is facile and widely applicable in the synthesis of a series of SAS catalysts including SAS-Fe, SAS-Ni, SAS-Cu, SAS-Zn, SAS-Ru, SAS-Rh, SAS-Pd, SAS-Pt, and SAS-Ir. The as-obtained SAS catalysts can be easily synthesized at gram scale and the metal loading of SAS-Fe catalysts achieves a record value of 30 wt%, which meets the requirement of practical applications. Moreover, it is discovered that SAS-Fe catalysts show unprecedented catalytic performance for epoxidation of styrene using O2 as the only oxidant (yield: 64%; selectivity: 89%), while Fe nanoparticles and ironporphyrin are inactive. This discovery is believed to pave the way for exploiting the unparalleled properties of SAS catalysts and promoting their industrial applications.

20.
Nano Lett ; 20(8): 6206-6214, 2020 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-32697097

RESUMO

Herein, we report efficient single copper atom catalysts that consist of dense atomic Cu sites dispersed on a three-dimensional carbon matrix with highly enhanced mesoporous structures and improved active site accessibility (Cu-SA/NC(meso)). The ratio of +1 to +2 oxidation state of the Cu sites in the Cu-SA/NC(meso) catalysts can be controlled by varying the urea content in the adsorption precursor, and the activity for ORR increases with the addition of Cu1+ sites. The optimal Cu1+-SA/NC(meso)-7 catalyst with highly accessible Cu1+ sites exhibits superior ORR activity in alkaline media with a half-wave potential (E1/2) of 0.898 V vs RHE, significantly exceeding the commercial Pt/C, along with high durability and enhanced methanol tolerance. Control experiments and theoretical calculations demonstrate that the superior ORR catalytic performance of Cu1+-SA/NC(meso)-7 catalyst is attributed to the atomically dispersed Cu1+ sites in catalyzing the reaction and the advantage of the introduced mesoporous structure in enhancing the mass transport.

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