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1.
Artigo em Inglês | MEDLINE | ID: mdl-38709409

RESUMO

Nonpoint source pollution (NPSP) has always been the dominant threat to regional waters. Based on empirical models of the revised universal soil loss equation and the phosphorus index, an NPSP risk assessment model denoted as SL-NPSRI was developed. The surface soil pollutant loss was estimated by simulating the rain-runoff topographic process, and the influence of path attenuation was quantified. A case study in the Yellow River Delta and corresponding field surveys of soil pollutants and water quality showed that the established model can be applied to evaluate the spatial heterogeneity of NPSP. NPSP usually occurs during high-intensity rainfall periods and in larger estuaries. Summer rainfall increased pollutant transport into the sea from late July to mid-August and caused estuarine dilution. Higher NPSP risks often correspond to coastal areas with lower vegetation coverage, higher soil erodibility, and higher soil pollutant concentrations. Agricultural NPSP originating from cropland significantly increase the pollutant fluxes. Therefore, area-specific land use management and vegetation coverage improvement, and temporal-specific strategies can be explored for NPSP control during source-transport hydrological processes. This research provides a novel insight for coastal NPSP simulations by comprehensively analyzing the soil erosion process and its associated pollutant loss effects, which can be useful for targeted spatiotemporal solutions.

2.
Nat Mater ; 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38769206

RESUMO

Structurally ordered L10-PtM (M = Fe, Co, Ni and so on) intermetallic nanocrystals, benefiting from the chemically ordered structure and higher stability, are one of the best electrocatalysts used for fuel cells. However, their practical development is greatly plagued by the challenge that the high-temperature (>600 °C) annealing treatment necessary for realizing the ordered structure usually leads to severe particle sintering, morphology change and low ordering degree, which makes it very difficult for the gram-scale preparation of desirable PtM intermetallic nanocrystals with high Pt content for practical fuel cell applications. Here we report a new concept involving the low-melting-point-metal (M' = Sn, Ga, In)-induced bond strength weakening strategy to reduce Ea and promote the ordering process of PtM (M = Ni, Co, Fe, Cu and Zn) alloy catalysts for a higher ordering degree. We demonstrate that the introduction of M' can reduce the ordering temperature to extremely low temperatures (≤450 °C) and thus enable the preparation of high-Pt-content (≥40 wt%) L10-Pt-M-M' intermetallic nanocrystals as well as ten-gram-scale production. X-ray spectroscopy studies, in situ electron microscopy and theoretical calculations reveal the fundamental mechanism of the Sn-facilitated ordering process at low temperatures, which involves weakened bond strength and consequently reduced Ea via Sn doping, the formation and fast diffusion of low-coordinated surface free atoms, and subsequent L10 nucleation. The developed L10-Ga-PtNi/C catalysts display outstanding performance in H2-air fuel cells under both light- and heavy-duty vehicle conditions. Under the latter condition, the 40% L10-Pt50Ni35Ga15/C catalyst delivers a high current density of 1.67 A cm-2 at 0.7 V and retains 80% of the current density after extended 90,000 cycles, which exceeds the United States Department of Energy performance metrics and represents among the best cathodic electrocatalysts for practical proton-exchange membrane fuel cells.

3.
Cytotherapy ; 2024 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-38625072

RESUMO

BACKGROUND AIMS: Chimeric antigen receptor-T (CAR-T) cells have exhibited remarkable efficacy in treating refractory or relapsed multiple myeloma (R/R MM). Although obesity has a favorable value in enhancing the response to immunotherapy, less is known about its predictive value regarding the efficacy and prognosis of CAR-T cell immunotherapy. METHODS: We conducted a retrospective study of 111 patients with R/R MM who underwent CAR-T cell treatment. Using the body mass index (BMI) classification, the patients were divided into a normal-weight group (73/111) and an overweight group (38/111). We investigated the effect of BMI on CAR-T cell therapy outcomes in patients with R/R MM. RESULTS: The objective remission rates after CAR-T cell infusion were 94.7% and 89.0% in the overweight and normal-weight groups, respectively. The duration of response and overall survival were not significant difference between BMI groups. Compared to normal-weight patients, overweight patients had an improved median progression-free survival. There was no significant difference in cytokine release syndrome and immune effector cell-associated neurotoxicity syndrome between the subgroups. In terms of hematological toxicity, the erythrocyte, hemoglobin, platelet, leukocyte and neutrophil recovery was accelerated in the overweight group. Fewer patients in the overweight group displayed moderate percent CD4 and CD4/CD8 ratios compared to the normal-weight group. Furthermore, the percent CD4 ratios were positively correlated with the levels of cytokines [interleukin-2 (IL-2) (day 14), interferon gamma (IFN-γ) (day 7) and tumor necrosis factor alpha (TNF-α) (days 14 and 21)] after cells infusion. On the other hand, BMI was positively associated with the levels of IFN-γ (day 7) and TNF-α (days 14 and 21) after CAR-T cells infusion. CONCLUSIONS: Overall, this study highlights the potential beneficial effect of a higher BMI on CAR-T cell therapy outcomes.

4.
Small Methods ; : e2400336, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38517268

RESUMO

Industrializing water electrolyzers demands better electrocatalysts, especially for the anodic oxygen evolution reaction (OER). The prevailing OER catalysts are Ir or Ru-based nanomaterials, however, they still suffer from insufficient stability. An alternative yet considerably less explored approach is to upgrade Rh, a known stable but moderately active element for OER electrocatalysis, via rational structural engineering. Herein, a precise synthesis of assembled RhRuFe trimetallenes (RhRuFe TMs) with an average thickness of 1 nm for boosting overall water splitting catalysis is reported. Favorable mass transport and optimized electronic structure collectively render RhRuFe TMs with an improved OER activity of an overpotential of 330 mV to deliver 10 mA cm-2, which is significantly lower than the Rh/C control (by 601 mV) and reported Rh-based OER electrocatalysts. In particular, the RhRuFe TMs-based water splitting devices can achieve the current density of 10 mA cm-2 at a low voltage of 1.63 V, which is among the best in the Rh-based bifunctional catalysts for electrolyzers. The addition of Fe in RhRuFe TMs can modulate the strain/electron distribution of the multi-alloy, which regulates the binding energies of H* and OH* in hydrogen and oxygen evolution reactions for achieving the enhanced bifunctional OER and HER catalysis is further demonstrated.

5.
Angew Chem Int Ed Engl ; 63(7): e202317987, 2024 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-38152839

RESUMO

Platinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well-known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low-electronegativity Mn-contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg-1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well-known high-electronegativity Ni-based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals' dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite-based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm-2 at a low Pt loading and high-performance retention over 50 h operations at 0.6 V in H2 -O2 hydrogen fuel cells.

6.
Bioresour Technol ; 386: 129566, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37506936

RESUMO

The nitrogen removal efficiency and distribution of microbial community in a denitrification process aided by zero-valent iron (ZVI) under low carbon-to-nitrogen ratio (C/N) were assessed in this study. Experimental results demonstrated that the nitrogen removal efficiency (TNRE) increased to 96.4 ± 2.72% and 63.3 ± 4.02% after continuous addition of ZVI with molar ratio of ZVI to nitrate (NO3--N) (ZVI/N) of 6 at C/N of 3 and 2, respectively, which was 4% and 7.7% higher than the blank one. Meanwhile, extracellular polymeric substance (EPS) could be used as electron transfer medium and endogenous carbon source for denitrification system and also the production of which increased by 28.43% and 53.10% under ZVI stimulation compared to the control group. Finally, a symbiotic system composed by autotrophic and heterotrophic denitrification bacteria was formed by aid of ZVI. This study proposed new insights into denitrification process improved by ZVI.


Assuntos
Carbono , Ferro , Desnitrificação , Nitrogênio , Matriz Extracelular de Substâncias Poliméricas , Nitratos , Reatores Biológicos
7.
Sci Rep ; 13(1): 3821, 2023 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-36882531

RESUMO

Aiming at the traditional ecological footprint model, the improved ecological footprint of the carbon footprint effectively makes up for the singularity of the ecological footprint's consideration of carbon emissions, and plays an important role in promoting high-quality development and ecological sustainability. This paper selects 2015, 2018 and 2020 as important time points for the study, corrects the ecological footprint parameter factors based on net primary productivity (NPP), measures the ecological footprint after the improvement of the carbon footprint, studies the spatial and temporal variation in the ecological footprint at the 100-m grid scale with the support of IPCC greenhouse gas inventory analysis, and analyzes the current ecological conservation status of the Yellow River Delta. Additionally, in the context of a low carbon economy, the decoupling index of carbon emissions and GDP is extended to the evaluation and analysis of high-quality development. The study showed that (1) the ecological footprint of the Yellow River Delta has increased year by year, from 0.721 hm2·person- 1 to 0.758 hm2·person- 1, an average annual increase of 2.9%; the ecological carrying capacity has decreased from 0.40 hm2·person- 1 to 0.31 hm2·person- 1, an overall decrease of 28.59%. (2) The overall ecological deficit of the Yellow River Delta grid is lightly overloaded, with most of the ecological surplus occurring in the northern and eastern parts of the study area and a few moderate and heavy overloads in the center of the core area where there is a lot of built-up land and the area is small and easy to gather. (3) Based on the low-carbon economy analysis, 2015, 2017 and 2020 reach absolute decoupling and are in the ideal scenario. However, in the rest of the years, carbon emissions and economic development are still in a large contradiction, and decoupling has fluctuated and varied greatly in the last six years. The effective combination of ecological footprint and low carbon economy analysis provides an important theoretical basis for improving ecological conservation and achieving high-quality development.

8.
BMC Med Genomics ; 16(1): 19, 2023 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-36737753

RESUMO

BACKGROUND: Thyroid carcinoma (THCA) is a malignant endocrine tumor all around the world, which is influenced by genetic and environmental factors. OBJECTIVE: To explore the association between TPO rs2048722, PTCSC2 rs925489, SEMA4G rs4919510 polymorphisms and THCA susceptibility in Chinese population. METHODS: We recruited 365 THCA patients and 498 normal controls for the study. Logistic regression analysis was used to evaluate the association between TPO rs2048722, PTCSC2 rs925489, SEMA4G rs4919510 polymorphisms and THCA susceptibility. MDR was used to assess the genetic interactions among the three SNPs. RESULTS: Overall analysis demonstrated that rs925489 of PTCSC2 was evidently associated with increased risk of THCA in multiple genetic models (OR = 1.59, 95%CI = 1.12-2.24, p = 0.009). The results of stratified analysis illustrated that rs2048722 of TPO can significantly increase the THCA susceptibility of participants less than or equal to 44 years old and smokers. Similarly, rs925489 of PTCSC2 obviously improved the risk of THCA among participants older than 44 years, males, smokers and drinkers. However, rs4919510 of SEMA4G has a protective effect on the development of THCA among participants with less than or equal to 44 years old and non-drinkers. Interestingly, there was a strong genetic interaction among the three SNPs in the occurrence of THCA risk. CONCLUSION: TPO rs2048722, PTCSC2 rs925489 and SEMA4G rs4919510 polymorphisms were evidently associated with the risk of THCA in the Chinese population, which was affected by age, gender, smoking and drinking consumption.


Assuntos
Predisposição Genética para Doença , Neoplasias da Glândula Tireoide , Masculino , Humanos , Neoplasias da Glândula Tireoide/genética , Neoplasias da Glândula Tireoide/patologia , Polimorfismo de Nucleotídeo Único , Povo Asiático/genética , Alelos
10.
Nat Commun ; 13(1): 3822, 2022 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-35780239

RESUMO

As the most well-known electrocatalyst for cathodic hydrogen evolution in water splitting electrolyzers, platinum is unfortunately inefficient for anodic oxygen evolution due to its over-binding with oxygen species and excessive dissolution in oxidative environment. Herein we show that single Pt atoms dispersed in cobalt hydrogen phosphate with an unique Pt(OH)(O3)/Co(P) coordination can achieve remarkable catalytic activity and stability for oxygen evolution. The catalyst yields a high turnover frequency (35.1 ± 5.2 s-1) and mass activity (69.5 ± 10.3 A mg-1) at an overpotential of 300 mV and excellent stability. Mechanistic studies elucidate that the superior catalytic performance of isolated Pt atoms herein stems from optimal binding energies of oxygen intermediate and also their strong electronic coupling with neighboring Co atoms that suppresses the formation of soluble Ptx>4 species. Alkaline water electrolyzers assembled with an ultralow Pt loading realizes an industrial-level current density of 1 A cm-2 at 1.8 volts with a high durability.

11.
Front Microbiol ; 13: 885015, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35495717

RESUMO

Porcine reproductive and respiratory syndrome virus (PRRSV) causes tremendous economic losses to the swine industry worldwide. In China, novel PRRSVs have frequently emerged in recent years, but the evolutionary relationship among these viruses has remained unclear. In the present study, a 4-year PRRSV genome-monitoring study was performed on samples from a pig farm. We observed that NADC30-like PRRSVs with higher mutation rates replaced HP-PRRSVs as the epidemic strains. We monitored the variation in the same PRRSV strain evolved in a pig herd over 2 years and observed that the low genomic similarity of NADC30-like PRRSVs results from rapid mutation. We also showed that recombination events between NADC30-like and QYYZ-like PRRSVs resulted in the complex recombination patterns of PRRSVs, which have formed gradually over time. Furthermore, recombination of the same strain can occur at different locations and increase the diversity of recombination events. Overall, these findings interpret the evolutionary patterns of novel and emerging PRRSVs, information that is crucial for PRRSV control.

12.
Adv Mater ; 33(41): e2103762, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34423488

RESUMO

A crucial issue restricting the application of direct alcohol fuel cells (DAFCs) is the low activity of Pt-based electrocatalysts for alcohol oxidation reaction caused by the reaction intermediate (CO*) poisoning. Herein, a new strategy is demonstrated for making a class of sub-monolayer YOx /MoOx -surface co-decorated ultrathin platinum nanowires (YOx /MoOx -Pt NWs) to effectively eliminate the CO poisoning for enhancing methanol oxidation electrocatalysis. By adjusting the amounts of YOx and MoOx decorated on the surface of ultrathin Pt NWs, the optimized 22% YOx /MoOx -Pt NWs achieve a high specific activity of 3.35 mA cm-2 and a mass activity of 2.10 A mgPt -1 , as well as the enhanced stability. In situ Fourier transform infrared (FTIR) spectroscopy and CO stripping studies confirm the contribution of YOx and MoOx to anti-CO poisoning ability of the NWs. Density functional theory (DFT) calculations further reveal that the surface Y and Mo atoms with oxidation states allow COOH* to bind the surface through both the carbon and oxygen atoms, which can lower the free energy barriers for the oxidation of CO* into COOH*. The optimal NWs also show the superior activities toward the electro-oxidation of ethanol, ethylene glycol, and glycerol.

13.
Nano Lett ; 21(13): 5774-5781, 2021 07 14.
Artigo em Inglês | MEDLINE | ID: mdl-34187162

RESUMO

The high-valence metal catalysts show extraordinary talent in various electrochemical reactions. However, there is no facile method to synthesize high-valence noble metal-based materials. Herein, we synthesized the different high valence noble metal M-incorporated PdCu nanoparticles (M = Ir, Ru, Rh) by the assistant of Fe3+ and exhibit excellent performance for water electrolysis. In 0.1 M KOH, the OER and HER mass activities of Ir16-PdCu/C were 50.5 and 16.5 times as much as PdCu/C, and achieved a current density of 10 mA cm-2 at 1.63 V when worked for overall water splitting. DFT calculation revealed that the incorporating of high valence Ir could optimize the binding energy of the intermediate products, and promote the evolution of oxygen and hydrogen. Ex situ XPS shows that the huge amount of oxidized Ir (V) formed in OER could promote the formation of O-O bonds.


Assuntos
Eletrólise , Água , Catálise , Hidrogênio , Oxigênio
14.
Nano Lett ; 21(10): 4262-4269, 2021 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-33962514

RESUMO

Single-atom catalysts (SACs) exhibit great potential in heterogeneous catalysis. However, the achievement of obtaining high-loading SACs remains a bottleneck. Herein, we first demonstrate a unique gas-migration, trapping, and emitting strategy for building a kind of Cd-based SAC for CO2 reduction (CO2RR). The gas-migration and trapping processes (≤750 °C) endows the material with an ultrahigh Cd loading amount of 30.3 wt %, while the emitting process can facilely modulate the loading amount from 30.3 to 1.4 wt %. For the CO2RR, the Cd-NC SACs with a loading amount of 18.4 wt % exhibits the maximum Faraday efficiency of 91.4% for CO at -0.728 V. The operando infrared spectroscopy studies prove the presence of main intermediates *COO-, *COOH, and *CO on Cd-NC-5M SACs during the catalytic process, indicating that the CO2RR follows the proton-decoupled electron-transfer mechanism. Density functional theory simulations reveal that the Cd-N4 structure reduces the Gibbs free energy of the rate-determining step (the hydrogenation step of *COOH).

15.
Sci Bull (Beijing) ; 66(1): 44-51, 2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-36654312

RESUMO

The performance of fuel-cell related electrocatalysis is highly dependent on the morphology, size and composition of a given catalyst. In terms of rational design of Pt-based catalyst, one-dimensional (1D) ultrafine Pt alloy nanowires (NWs) are considered as a commendable model for enhanced catalysis on account of their favorable mass/charge transfer and structural durability. However, in order to achieve the noble metal catalysts in higher efficiency and lower cost, building high-index facets and shaping hollow interiors should be integrated into 1D Pt alloy NWs, which has rarely been done so far. Here, we report the first synthesis of a class of spiny Pd/PtFe core/shell nanotubes (SPCNTs) constructed by cultivating PtFe alloy branches with rich high-index facets along the 1D removable Pd supports, which is driven by the galvanic dissolution of Pd substrates concomitant with Stranski-Krastanov (S-K) growth of Pt and Fe, for achieving highly efficient fuel-cells-related electrocatalysis. This new catalyst can even deliver electrochemical active surface area (ECSA) of 62.7 m2 gPt-1, comparable to that of commercial carbon-supported Pt nanoparticles. With respect to oxygen reduction catalysis, the SPCNTs showcase the remarkable mass and specific activity of 2.71 A mg-1 and 4.32 mA cm-2, 15.9 and 16.0 times higher than those of commercial Pt/C, respectively. Also, the catalysts exhibit extraordinary resistance to the activity decay and structural degradation during 50,000 potential cycles. Moreover, the SPCNTs serve as a category of efficient and stable catalysts towards anodic alcohol oxidation.

16.
Virus Genes ; 56(5): 673, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32594295

RESUMO

The original version of this article unfortunately contained an error in GenBank Accession Number.

17.
Virus Genes ; 56(3): 354-360, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32198605

RESUMO

Seven strains of porcine reproductive and respiratory syndrome virus (PRRSV) were isolated from 2014 to 2017 in the Shandong province of China and their genomes were sequenced and analyzed. Results showed that all seven of the isolates belong to PRRSV 2, and are clustered into four lineages (lineage 1, 3, 5 and 8) based on comparisons of the ORF5 gene. Comparative analysis of genomes and specific amino acid sites revealed that three of the strains (SDwh1402, SDwh1602 and SDwh1701) have evolved directly from modified live virus (MLV) JXA1-P80, TJM-F92 and IngelvacPRRS. Further recombination analysis revealed that two of the strains (SDyt1401 and SDwh1601) were the result of a recombination event between MLVs JXA1-P80 and NADC30 while two other strains (SDwh1403 and SDqd1501) were the result of recombination between MLVs IngelvacPRRS and NADC30 and HP-PRRSV and QYYZ, respectively. Our results add to the data on MLV evolution and PRRSV recombination and provide a better understanding of the epidemiology of PRRSV in China.


Assuntos
Evolução Molecular , Variação Genética , Síndrome Respiratória e Reprodutiva Suína/epidemiologia , Síndrome Respiratória e Reprodutiva Suína/virologia , Vírus da Síndrome Respiratória e Reprodutiva Suína/genética , Recombinação Genética , Animais , China/epidemiologia , Genoma Viral , Genômica/métodos , Filogenia , Vírus da Síndrome Respiratória e Reprodutiva Suína/isolamento & purificação , Suínos
18.
Sci Bull (Beijing) ; 65(2): 97-104, 2020 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-36659084

RESUMO

Highly-branched dendritic Pt-based nanocrystals possess great potential in catalyzing the oxygen reduction reaction (ORR), but encounter performance ceiling due to their poor thermal and electrochemical stability. Here, we present a novel PtFe nanodendrites (NDs) branched with two-dimensional (2D) twinned nanoplates rather than conventional 1D nanowires, which breaks the ORR performance ceiling of dendritic catalysts by inducing the unique Pt-skin configuration via rationally thermal treatment. By further hybridizing the Pt-skin PtFe NDs/C with amino-functionalized ionic liquids (ILs), we achieve an unprecedented mass activity of 3.15 A/mgPt at 0.9 V versus reversible hydrogen electrode (RHE) in the PtFe-based ORR electrocatalytic system. They also show excellent electrocatalytic durability for ORR with negligible activity decay and no apparent structural change after 20,000 cycles, in sharp contrast to the nanowires branched PtFe NDs counterpart. The remarkable catalytic performance is attributed to a combination of several structural features, including 2D morphology, twin boundary, partially ordered phase and strong coordination with amino group. This work highlights the significance of stabilizing electrocatalytic structures via morphology tuning, which thus enables further surface and interface modification for performance breakthrough in ORR electrocatalysis.

19.
Chemistry ; 26(18): 4032-4038, 2020 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-31769895

RESUMO

Searching for new anti-poisoning Pt-based catalysts with enhanced activity for alcohol oxidation is the key in direct alcohol fuel cells (DAFCs). However, in the traditional strategy for designing bimetallic or multimetallic alloy is still difficult to achieve a satisfactory heterogeneous electrocatalyst because the activity often depends on only the surface atoms. Herein, we fabricate the multicomponent active sites by creating a sulfide structure on 1D PtNiCo trimetallic nanowires (NWs), to give a PtNiCo/NiCoS interface NWs (IFNWs). Owing to the presence of sulfide interfaces, the PtNiCo/NiCoS IFNWs enable an impressive methanol/ethanol oxidation reaction (MOR/EOR) performance and excellent anti-CO poisoning tolerance. They have the MOR and EOR mass activities of 2.25 Amg-1 Pt and 1.62 Amg-1 Pt , around 1.26, 3.21 and 1.46, 2.96 times higher than those of PtNiCo NWs and commercial Pt/C, respectively. CO-stripping and XPS measurements further demonstrate that the new interfacial structure and optimal bonding of Pt-CO can result in accelerating the removal of surface adsorbed carbonaceous intermediates. Moreover, such a unique structure has also demonstrated a much-improved ability for the electrochemical detection of some important molecules (H2 O2 and NH2 NH2 ).

20.
Nature ; 574(7776): 81-85, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31554968

RESUMO

The efficient interconversion of chemicals and electricity through electrocatalytic processes is central to many renewable-energy initiatives. The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER)1-4 has long posed one of the biggest challenges in this field, and electrocatalysts based on expensive platinum-group metals are often required to improve the activity and durability of these reactions. The use of alloying5-7, surface strain8-11 and optimized coordination environments12 has resulted in platinum-based nanocrystals that enable very high ORR activities in acidic media; however, improving the activity of this reaction in alkaline environments remains challenging because of the difficulty in achieving optimized oxygen binding strength on platinum-group metals in the presence of hydroxide. Here we show that PdMo bimetallene-a palladium-molybdenum alloy in the form of a highly curved and sub-nanometre-thick metal nanosheet-is an efficient and stable electrocatalyst for the ORR and the OER in alkaline electrolytes, and shows promising performance as a cathode in Zn-air and Li-air batteries. The thin-sheet structure of PdMo bimetallene enables a large electrochemically active surface area (138.7 square metres per gram of palladium) as well as high atomic utilization, resulting in a mass activity towards the ORR of 16.37 amperes per milligram of palladium at 0.9 volts versus the reversible hydrogen electrode in alkaline electrolytes. This mass activity is 78 times and 327 times higher than those of commercial Pt/C and Pd/C catalysts, respectively, and shows little decay after 30,000 potential cycles. Density functional theory calculations reveal that the alloying effect, the strain effect due to the curved geometry, and the quantum size effect due to the thinness of the sheets tune the electronic structure of the system for optimized oxygen binding. Given the properties and the structure-activity relationships of PdMo metallene, we suggest that other metallene materials could show great promise in energy electrocatalysis.

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