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1.
Se Pu ; 42(3): 282-290, 2024 Mar 08.
Artigo em Chinês | MEDLINE | ID: mdl-38503705

RESUMO

Saussurea costus, a perennial herb belonging to the Asteraceae family, is a vital ingredient in traditional Chinese medicine. Increased demands for the herb have led to its widespread cultivation in China, but the corresponding increase in pesticide use has raised concerns about pesticide residues. Such residues would affect the safety and global market potential of Saussurea costus. Thus, a simple method is crucial to detect pesticide residues. The QuEChERS technique, in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS), is commonly used for residue detection. However, traditional adsorbents may be unable to purify complex herbal mixtures well, affecting accuracy and instrument performance. Choosing suitable purification materials for Saussurea costus samples with complex matrices is of significant importance. This study focused on the detection of 35 prohibited pesticides in Saussurea costus. A rapid detection method was established by combining the QuEChERS technique with GC-MS/MS and utilizing a combination of multiwalled carbon nanotubes (MWCNTs), octadecylsilane-bonded silica gel (C18), and anhydrous magnesium sulfate (MgSO4) as the purification adsorbent. The samples were extracted with acetonitrile, purified by an improved QuEChERS process, subjected to GC-MS/MS analysis in multiple reaction monitoring (MRM) mode, and quantified using the internal standard method. The purification effects of four materials (C18, MWCNTs, N-propyl ethylenediamine (PSA), and graphitized carbon black (GCB)) and their optimal dosages were investigated by considering the matrix characteristics of the samples. An orthogonal experimental design was employed to optimize the ratio of adsorbent combinations, and the optimal adsorbent combination was determined to be 450 mg of MgSO4, 400 mg of C18, and 50 mg of MWCNTs. Matrix effect (ME) evaluation of the S. costus matrix showed that 31 target compounds strongly exhibited matrix-enhancement effects. Thus, matrix-matched calibration was employed in this study. Methodological investigation revealed that the standard curves for the 35 pesticides exhibited good linearity, with correlation coefficients (r2) greater than 0.9970. The average recoveries at three spiked levels ranged from 69.6% to 126.9%, and the relative standard deviations (RSDs) for parallel groups were all less than 10%. The limits of detection (LODs) and quantification (LOQs) ranged from 0.2 to 5.4 µg/kg and from 0.6 to 18.1 µg/kg, respectively. The developed method was used to screen and detect 35 pesticide residues in 20 batches of S. costus samples, and the target compounds were detected in six batches. The proposed method is simple, sensitive, and accurate. Thus, it is suitable for the rapid screening and detection of the 35 pesticide residues in S. costus and provides technical support for the cultivation, production, and quality control of the herb.


Assuntos
Nanotubos de Carbono , Resíduos de Praguicidas , Saussurea , Espectrometria de Massas em Tandem/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Nanotubos de Carbono/análise , Nanotubos de Carbono/química , Resíduos de Praguicidas/análise
2.
J Orthop Surg Res ; 19(1): 35, 2024 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-38183142

RESUMO

BACKGROUND: In this study, we compared the clinical efficacy of endoscope-assisted anterior cervical discectomy and fusion (ACDF) with open ACDF in the treatment of single-segment cervical spondylotic myelopathy. METHODS: A retrospective analysis was performed on 52 patients with single-segment cervical spondylotic myelopathy between June 2021 and February 2022, including 33 males and 19 females, with a mean age of 58.42 ± 9.26) years. Among them, 28 patients were treated with endoscope-assisted ACDF (Group A), including 2 cases of C4/5 segment, 16 cases of C5/6 segment, and 10 cases of C6/7 segment; 24 patients were treated with open ACDF (Group B), including 4 cases of C4/5 segment, 11 cases of C5/6 segment, and 9 cases of C6/7 segment. The operation time, intraoperative blood loss, hospital stay, and complications were recorded and compared between the two groups. The Visual Analogue Scale (VAS) and the Japanese Orthopaedic Association (JOA) score were used for clinical evaluation during the follow-up in the 1st month and 3rd month after surgery, and at the final follow-up. RESULTS: The 52 patients were followed up on average for 13.04 months (12-17 months). The operation time in Group A and Group B was (105.18 + 8.66) minutes and (81.88 + 6.05) minutes, the intraoperative blood loss was (84.29 + 13.45) mL and (112.92 + 17.81) mL, and the hospital stay was (6.75 + 1.29) days and (7.63 + 1.41) days, respectively. The difference between the two groups was statistically significant (P < 0.05). The VAS and JOA scores in the 1st month and the 3rd month after surgery and the last follow-up significantly improved in both groups compared with those before surgery (P < 0.05). The VAS and JOA scores of Group A in the 1st month, 3rd month after surgery, and the last follow-up were better than those in Group B (P < 0.05). The complication rate in Group A was 7% (2/28), which was not significantly different from the 17% (4/24) in Group B (P > 0.05). CONCLUSION: Both endoscope-assisted ACDF and open ACDF can achieve satisfactory clinical efficacy in the treatment of single-segment cervical spondylotic myelopathy. Although the operation time of endoscope-assisted ACDF is prolonged, it has the advantages of clear vision, thorough decompression, less blood loss, and reduced risk of nerve damage, and is worthy of clinical promotion and application.


Assuntos
Perda Sanguínea Cirúrgica , Doenças da Medula Espinal , Feminino , Masculino , Humanos , Pessoa de Meia-Idade , Idoso , Estudos Retrospectivos , Doenças da Medula Espinal/diagnóstico por imagem , Doenças da Medula Espinal/cirurgia , Discotomia , Endoscópios
3.
Angew Chem Int Ed Engl ; 63(7): e202316762, 2024 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-38038365

RESUMO

Understanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during and after dynamic structural evolution on the OER activity of Fe-Ni (oxy)hydroxide catalysts using operando X-ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye-Waller factors obtained from extended X-ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. The enhanced OER activity of in situ-generated metal (oxy)hydroxides derived from different pre-catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy-conversion systems.

4.
Huan Jing Ke Xue ; 44(8): 4497-4506, 2023 Aug 08.
Artigo em Chinês | MEDLINE | ID: mdl-37694644

RESUMO

The effects of coconut fiber biochar (CFB) and nitrate-modified coconut fiber biochar (NCFB) on the passivation of exogenous lead (Pb) in paddy soils and their underlying mechanisms were investigated using soil incubation experiments combined with spectroscopic techniques such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray fluorescence (SRXRF), and Fourier transform infrared absorption spectroscopy (FTIR). The effects of NCFB and CFB on the passivation of exogenous lead (Pb) in paddy soils and its underlying mechanisms were investigated. Compared with that of CFB, the inner wall of NCFB honeycomb pores was rougher, and the amount of alcohol-phenol-ether functional groups containing the C-O structure and the amount of carboxyl groups containing the C[FY=,1]O/O[FY=,1]C-O structure on the surface of CFB was significantly decreased after nitric acid modification. Compared with that in the control (without biochar) paddy soil after 150 d of incubation, the EDTA-extracted Pb content in the paddy soil with CFB and NCFB was reduced by 39.7% and 105.4%, respectively. The carbonate-bound and Fe-Mn oxide-bound Pb contents were significantly lower, and the organic-bound and residue Pb contents were significantly higher in the NCFB-added soil. The SRXRF scans showed that the exogenous Pb was enriched in the microregions of CFB particles rich in Ca and Cu elements and relatively less so in the microregions of soil aggregates rich in the Fe, Mn, and Ti elements. In addition, the characteristic peaks of carboxylates (1384 cm-1) in A-CFBPb and A-NCFBPb were significantly enhanced in the incubation experiment in the presence of exogenous Pb compared to A-CFB and A-NCFB in the absence of exogenous Pb. The addition of CFB or NCFB was more effective in passivating exogenous Pb in paddy soils and promoted the gradual transformation of Pb from unstable to more stable forms in paddy soils to achieve the effect of passivating Pb. The greater amount of carboxyl functional groups in NCFB participated in the passivation of exogenous Pb, which made NCFB more effective than CFB in passivating Pb. NCFB was more effective than CFB in passivating exogenous Pb in paddy soils due to its rougher inner walls of honeycomb pores and abundant carboxyl functional groups. In tropical areas such as Hainan, coconut fiber biochar and its modification can be considered as an environmentally friendly candidate method for the remediation of soil Pb contamination.


Assuntos
Cocos , Nitratos , Chumbo , Ácido Nítrico
5.
Sci Adv ; 9(26): eadh1320, 2023 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-37379398

RESUMO

Manipulating the intrinsic activity of heterogeneous catalysts at the atomic level is an effective strategy to improve the electrocatalytic performances but remains challenging. Here, atomically dispersed Ni anchored on CeO2 particles entrenched on peanut-shaped hollow nitrogen-doped carbon structures (a-Ni/CeO2@NC) is rationally designed and synthesized. The as-prepared a-Ni/CeO2@NC catalyst exhibits substantially boosted intrinsic activity and greatly reduced overpotential for the electrocatalytic oxygen evolution reaction. Experimental and theoretical results demonstrate that the decoration of isolated Ni species over the CeO2 induces electronic coupling and redistribution, thus resulting in the activation of the adjacent Ce sites around Ni atoms and greatly accelerated oxygen evolution kinetics. This work provides a promising strategy to explore the electronic regulation and intrinsic activity improvement at the atomic level, thereby improving the electrocatalytic activity.

6.
Small ; 19(25): e2301235, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-36922746

RESUMO

Here, an ultra-highly active Ni-MOF-5 catalyst with high Ni loading for ethylene dimerization is reported. The Ni-MOF-5 catalysts are synthesized by a facile one-pot co-precipitation method at room temperature, where Ni2+ replaces Zn2+ in MOF-5. Unlike Zn2+ with tetrahedral coordination in MOF-5, Ni2+ is coordinated with extra solvent molecules except for four-oxygen from the framework. After removing coordinated solvent molecules, Ni-MOF-5 achieves an ethylene turnover frequency of 352 000 h-1 , corresponding to 9040 g of product per gram of catalyst per hour, at 35 °C and 50 bar, far exceeding the activities of all reported heterogeneous catalysts. The high Ni loading and full exposure structure account for the excellent catalytic performance. Isotope labeling experiments reveal that the catalytic process follows the Cossee-Arlman mechanism, rationalizing the high activity and selectivity of the catalyst. These results demonstrate that Ni-MOF-5 catalysts are very promising for industrial catalytic ethylene dimerization.

7.
Adv Mater ; 35(19): e2207888, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36921278

RESUMO

Hybrid materials, integrating the merits of individual components, are ideal structures for efficient oxygen evolution reaction (OER). However, the rational construction of hybrid structures with decent physical/electrochemical properties is yet challenging. Herein, a promising OER electrocatalyst composed of trimetallic metal-organic frameworks supported over S/N-doped carbon macroporous fibers (S/N-CMF@Fex Coy Ni1-x-y -MOF) via a cation-exchange strategy is delicately fabricated. Benefiting from the trimetallic composition with improved intrinsic activity, hollow S/N-CMF matrix facilitating exposure of active sites, as well as their robust integration, the resultant S/N-CMF@Fex Coy Ni1-x-y -MOF electrocatalyst delivers outstanding activity and stability for alkaline OER. Specifically, it needs an overpotential of 296 mV to reach the benchmark current density of 10 mA cm-2 with a small Tafel slope of 53.5 mV dec-1 . In combination with X-ray absorption fine structure spectroscopy and density functional theory calculations, the post-formed Fe/Co-doped γ-NiOOH during the OER operation is revealed to account for the high OER performance of S/N-CMF@Fex Coy Ni1-x-y -MOF.

8.
Faraday Discuss ; 242(0): 429-442, 2023 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-36173024

RESUMO

Activity, cost, and durability are the trinity of catalysis research for the electrochemical oxygen reduction reaction (ORR). While studies towards increasing activity and reducing cost of ORR catalysts have been carried out extensively, much effort is needed in durability investigation of highly active ORR catalysts. In this work, we examined the stability of a trimetallic PtPdCu catalyst that has demonstrated high activity and incredible durability during ORR using density functional theory (DFT) based computations. Specifically, we studied the processes of dissolution/deposition and diffusion between the surface and inner layer of Cu species of Pt20Pd20Cu60 catalysts at electrode potentials up to 1.2 V to understand their role towards stabilizing Pt20Pd20Cu60 catalysts. The results show there is a dynamic Cu surface composition range that is dictated by the interplay of the four processes, dissolution, deposition, diffusion from the surface to inner layer, and diffusion from the inner layer to the surface of Cu species, in the stability and observed oscillation of lattice constants of Cu-rich PtPdCu nanoalloys.

9.
World J Clin Cases ; 11(36): 8512-8518, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38188214

RESUMO

BACKGROUND: Sarcoidosis is a multisystem disease characterized by granuloma formation in various organs. Sarcoidosis-related flexor tendon contractures are uncommon in clinical settings. This contracture is similar to stenosing tenosynovitis and potentially leads to misdiagnosis and mistreatment. Herein, we report a rare case of sarcoidosis-related finger flexor tendon contracture that was misdiagnosed as tenosynovitis. CASE SUMMARY: A 44-year-old woman presented to our department with flexion contracture of the right ring and middle fingers. The patient was misdiagnosed with tenosynovitis and underwent acupotomy release of the A1 pulley of the middle finger in another hospital that resulted in iatrogenic rupture of both the superficial and profundus flexors. Radiological presentation showed multiple sarcoid involvements in the pulmonary locations and ipsilateral forearm. A diagnosis of sarcoidosis was made based on the presence of non-caseating granulomas with tubercles consisting of Langhans giant cells with lymphocyte infiltration on biopsy, and the patient underwent surgical repair for the contracture. After 2 mo, the patient experienced another spontaneous rupture of the repaired middle finger tendon and underwent surgical re-repair. Satisfactory results were achieved at the 10 mo follow-up after reoperation. CONCLUSION: Sarcoidosis-related finger contractures are rare; thus, caution should be exercised when dealing with such patients to avoid incorrect treatment.

10.
Nat Commun ; 13(1): 4857, 2022 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-35982055

RESUMO

Copper (Cu)-based catalysts generally exhibit high C2+ selectivity during the electrochemical CO2 reduction reaction (CO2RR). However, the origin of this selectivity and the influence of catalyst precursors on it are not fully understood. We combine operando X-ray diffraction and operando Raman spectroscopy to monitor the structural and compositional evolution of three Cu precursors during the CO2RR. The results indicate that despite different kinetics, all three precursors are completely reduced to Cu(0) with similar grain sizes (~11 nm), and that oxidized Cu species are not involved in the CO2RR. Furthermore, Cu(OH)2- and Cu2(OH)2CO3-derived Cu exhibit considerable tensile strain (0.43%~0.55%), whereas CuO-derived Cu does not. Theoretical calculations suggest that the tensile strain in Cu lattice is conducive to promoting CO2RR, which is consistent with experimental observations. The high CO2RR performance of some derived Cu catalysts is attributed to the combined effect of the small grain size and lattice strain, both originating from the in situ electroreduction of precursors. These findings establish correlations between Cu precursors, lattice strains, and catalytic behaviors, demonstrating the unique ability of operando characterization in studying electrochemical processes.

11.
Adv Mater ; 34(23): e2200180, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35262973

RESUMO

2D materials show many particular properties, such as high surface-to-volume ratio, high anisotropic degree, and adjustable chemical functionality. These unique properties in 2D materials have sparked immense interest due to their applications in photocatalytic systems, resulting in significantly enhanced light capture, charge-transfer kinetics, and surface reaction. Herein, the research progress in 2D photocatalysts based on varied compositions and functions, followed by specific surface modification strategies, is introduced. Fundamental principles focusing on light harvesting, charge separation, and molecular adsorption/activation in the 2D-material-based photocatalytic system are systemically explored. The examples described here detail the use of 2D materials in various photocatalytic energy-conversion systems, including water splitting, carbon dioxide reduction, nitrogen fixation, hydrogen peroxide production, and organic synthesis. Finally, by elaborating the challenges and possible solutions for developing these 2D materials, the review is expected to provide some inspiration for the future research of 2D materials used on efficient photocatalytic energy conversions.

12.
ACS Appl Mater Interfaces ; 14(9): 11435-11447, 2022 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-35195398

RESUMO

The ability to harness the catalytic oxidation of hydrocarbons is critical for both clean energy production and air pollutant elimination, which requires a detailed understanding of the dynamic role of the nanophase structure and surface reactivity under the reaction conditions. We report here findings of an in situ/operando study of such details of a ternary nanoalloy under the propane oxidation condition using high-energy synchrotron X-ray diffraction coupled to atomic pair distribution function (HE-XRD/PDF) analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The catalysts are derived by alloying Pt with different combinations of second (Pd) and third (Ni) transition metals, showing a strong dependence of the catalytic activity on the Ni content. The evolution of the phase structure of the nanoalloy is characterized by HE-XRD/PDF probing of the lattice strain, whereas the surface activity is monitored by DRIFTS detection of the surface intermediate formation during the oxidation of propane by oxygen. The results reveal the dominance of the surface intermediate species featuring a lower degree of oxygenation upon the first C-C bond cleavage on the lower-Ni-content nanoalloy and a higher degree of oxygenation upon the second C-C bond cleavage on the higher-Ni-content nanoalloy. The face-centered-cubic-type phase structures of the nanoalloys under the oxidation condition are shown to exhibit Ni-content-dependent changes of lattice strains, featuring the strongest strain with little variation for the higher-Ni-content nanoalloy, in contrast to the weaker strains with oscillatory variation for the lower-Ni-content nanoalloys. This process is also accompanied by oxygenation of the metal components in the nanoalloy, showing a higher degree of oxygenation for the higher-Ni-content nanoalloy. These subtle differences in phase structure and surface activity changes correlate with the Ni-composition-dependent catalytic activity of the nanoalloys, which sheds a fresh light on the correlation between the dynamic change of atomic strains and the surface reactivity and has significant implications for the design of oxidation catalysts with enhanced activities.

13.
Environ Sci Pollut Res Int ; 29(4): 6347-6359, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34449023

RESUMO

Due to rapid population growth, industrialization, and urbanization, it is particularly important to address the increasingly serious ecological security issues in the process of urbanization, while it is important to grasp the impact of changes in land use structure on ecological security for scientific planning and to aid decision-making. As a typical valley basin industrialized city in northwest China, Lanzhou has complex geomorphology and climate with distinct regional characteristics, and the relationship between land use and ecological security is complex. In order to understand the current status and influencing factors of ecological security in various regions of Lanzhou, and to explore the intrinsic connection between ecological security and land use, this study constructed an ecological security evaluation index system based on the pressure-state-response (PSR) model with 14 secondary factors including natural, social, and economic factors. Based on the entropy method, GIS was used to analyze the trend of ecological security in each district and to clarify the coupling relationship between ecological security and land use change in Lanzhou City. The results show that the ecological security index (ESI) of Xigu District, a typical heavy industrial area, increased from 0.26 to 0.35, and the ESI of Yuzhong County, an agricultural development area, increased from 0.51 to 0.55 from 2000 to 2017. Low ESI was mainly distributed in areas with developed heavy industry, while high ESI was mainly found in areas with favorable natural conditions and mainly agricultural development. Economic factors were the leading factors affecting the ecological security of Lanzhou. In general, changes in land use structure and ecological security were inextricably linked, and the two influence and interact with each other. These results could provide some reference for the study of ecological security development and land use change in typical river valley cities and also provide a new path for other cities to study ecological security and the conservation of the ecological environment.


Assuntos
Conservação dos Recursos Naturais , Sistemas de Informação Geográfica , China , Cidades , Ecossistema , Entropia , Urbanização
14.
Sci Adv ; 7(46): eabk0919, 2021 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-34757786

RESUMO

Fundamental insights into the structural evolution of oxygen electrocatalysts under operating conditions are of substantial importance for designing efficient catalysts. Here, on the basis of operando x-ray absorption fine structure spectroscopy, we probe the in situ activation of Br-confined conductive Ni-based metal-organic framework (Br-Ni-MOF) hollow prisms toward an active oxygen electrocatalyst during the oxygen evolution reaction (OER) process. The successive structural transformations from pristine Br-Ni-MOF to a ß-Ni(OH)2 analog then subsequently to a γ-NiOOH phase during OER are observed. This post-formed γ-NiOOH analog manifests high OER performance with a superior overpotential of 306 mV at 10 mA cm−2 and a high turnover frequency value of 0.051 s−1 at an overpotential of 300 mV, making Br-Ni-MOF one of the most active oxygen electrocatalysts reported. Density functional theory calculations reveal that the strong electronic coupling between Br and Ni atoms accelerates the generation of the key *O intermediate toward fast OER kinetics.

15.
Angew Chem Int Ed Engl ; 60(50): 26397-26402, 2021 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-34661372

RESUMO

The development of efficient oxygen electrocatalysts and understanding their underlying catalytic mechanism are of significant importance for the high-performance energy conversion and storage technologies. Herein, we report novel CoCu-based bimetallic metal-organic framework nanoboxes (CoCu-MOF NBs) as promising catalysts toward efficient electrochemical oxygen evolution reaction (OER), fabricated via a successive cation and ligand exchange strategy. With the highly exposed bimetal centers and the well-designed architecture, the CoCu-MOF NBs show excellent OER activity and stability, with a small overpotential of 271 mV at 10 mA cm-2 and a high turnover frequency value of 0.326 s-1 at an overpotential of 300 mV. In combination of quasi in situ X-ray absorption fine structure spectroscopy and density-functional theory calculations, the post-formed CoCu-based oxyhydroxide analogue during OER is believed to account for the high OER activity of CoCu-MOF NBs, where the electronic synergy between Co and neighbouring Cu atoms promotes the O-O bond coupling toward fast OER kinetics.

16.
Adv Mater ; 33(40): e2103004, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34418171

RESUMO

Non-noble-metal-based nanomaterials can exhibit extraordinary electrocatalytic performance toward the oxygen evolution reaction (OER) by harnessing the structural evolution during catalysis and the synergistic effect between elements. However, the structure of active centers in bimetallic/multimetallic catalysts is under long-time debate in the catalysis community. Here, an efficient bimetallic Ni-Fe selenide-derived OER electrocatalyst is reported and the structure-activity correlation during the OER evolution studied. By combining experiments and theoretical calculations, a conceptual advance is provided, in that the local coordination structure distortion and disordering of active sites inherited from the pre-catalyst and post-formed by a further reconstruction are responsible for boosting the OER performance. The active center is identified on Ni sites showing moderate bindings with oxygenous intermediates rather than Fe sites with strong and poisonous adsorptions. These findings provide crucial understanding in manipulating the local coordination and electronic structures toward rational design and fabrication of efficient OER electrocatalysts.

17.
Angew Chem Int Ed Engl ; 60(35): 19068-19073, 2021 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-34137497

RESUMO

Highly efficient electrocatalysts are essential for the production of green hydrogen from water electrolysis. Herein, a metal-organic framework-assisted pyrolysis-replacement-reorganization approach is developed to obtain ultrafine Pt-Co alloy nanoparticles (sub-10 nm) attached on the inner and outer shells of porous nitrogen-doped carbon nanotubes (NCNT) with closed ends. During the thermal reorganization, the migration of Pt-Co nano-alloys to both surfaces ensures the maximized exposure of active sites while maintaining the robust attachment to the porous carbon matrix. Density functional theory calculations suggest a nearly thermodynamically-neutral free energy of adsorption for hydrogen intermediates and diversified active sites induced by alloying, thus resulting in a great promotion in intrinsic activity towards the hydrogen evolution reaction (HER). Benefiting from the delicate structural design and compositional modulation, the optimized Pt3 Co@NCNT electrocatalyst manifests outstanding HER activity and superior stability in both acidic and alkaline media.

18.
Sci Adv ; 7(21)2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-34020959

RESUMO

Lithium metal has been considered as an ideal anode candidate for future high energy density lithium batteries. Herein, we develop a three-dimensional (3D) hybrid host consisting of Ag nanoparticle-embedded nitrogen-doped carbon macroporous fibers (denoted as Ag@CMFs) with selective nucleation and targeted deposition of Li. The 3D macroporous framework can inhibit the formation of dendritic Li by capturing metallic Li in the matrix as well as reducing local current density, the lithiophilic nitrogen-doped carbons act as homogeneous nucleation sites owing to the small nucleation barrier, and the Ag nanoparticles improve the Li nucleation and growth behavior with the reversible solid solution-based alloying reaction. As a result, the Ag@CMF composite enables a dendrite-free Li plating/stripping behavior with high Coulombic efficiency for more than 500 cycles. When this anode is coupled with a commercial LiFePO4 cathode, the assembled full cell manifests high rate capability and stable cycling life.

19.
Adv Mater ; 33(50): e2006292, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33749011

RESUMO

The rapid progress of proton exchange membrane fuel cells (PEMFCs) and alkaline exchange membrane fuel cells (AMFCs) has boosted the hydrogen economy concept via diverse energy applications in the past decades. For a holistic understanding of the development status of PEMFCs and AMFCs, recent advancements in electrocatalyst design and catalyst layer optimization, along with cell performance in terms of activity and durability in PEMFCs and AMFCs, are summarized here. The activity, stability, and fuel cell performance of different types of electrocatalysts for both oxygen reduction reaction and hydrogen oxidation reaction are discussed and compared. Research directions on the further development of active, stable, and low-cost electrocatalysts to meet the ultimate commercialization of PEMFCs and AMFCs are also discussed.

20.
Angew Chem Int Ed Engl ; 60(21): 11841-11846, 2021 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-33739587

RESUMO

The development of efficient and low-cost electrocatalysts toward the oxygen evolution reaction (OER) is critical for improving the efficiency of several electrochemical energy conversion and storage devices. Here, we report an elaborate design and synthesis of porous Co-based trimetallic spinel oxide nanoboxes (NiCo2-x Fex O4 NBs) by a novel metal-organic framework engaged strategy, which involves chemical etching, cation exchange, and subsequent thermal oxidation processes. Owing to the structural and compositional advantages, the optimized trimetallic NiCo2-x Fex O4 NBs (x is about 0.117) deliver superior electrocatalytic performance for OER with an overpotential of 274 mV at 10 mA cm-2 , a small Tafel slope of 42 mV dec-1 , and good stability in alkaline electrolyte, which is much better than that of Co-based bi/monometallic spinel oxides and even commercial RuO2 .

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