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1.
J Colloid Interface Sci ; 667: 44-53, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38615622

RESUMO

The construction of high-asymmetrical structures demonstrates significant potential in improving the functionality and distinctness of nanomaterials, but remains a considerable challenge. Herein, we develop a one-pot method to fabricate regioselective super-assembly of Prussian blue analogue (PBA) -- a PBA anisotropic structure (PBA-AS) decorated with epitaxial modules--using a step-by-step epitaxial growth on a rapidly self-assembled cubic substrate guided by thiocyanuric acid (TCA) molecules. The epitaxial growth units manifest as diverse geometric shapes, which are predominantly concentrated on the {100}, {111}, or {100}+{111} crystal plane of the cubic substrate. The crystal plane and morphology of epitaxial module can be regulated by changing the TCA concentration and reaction temperature, enabling a high level of controllability over specific assembly sites and structures. To illustrate the advantage of the asymmetrical structure, phosphated PBA-AS demonstrates improved performance in the oxygen evolution reaction compared to simple phosphated PBA nanocube. This method offers valuable insights for designing asymmetrical nanomaterials with intricate architectures and versatile functionalities.

2.
Small ; : e2311267, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38534041

RESUMO

The controllable construction of complex metal-organic coordination polymers (CPs) merits untold scientific and technological potential, yet remains a grand challenge of one-step construction and modulating simultaneously valence states of metals and topological morphology. Here, a thiocyanuric acid (TCA)-triggered strategy is presented to one-step rapid synthesis a double-crystalline Prussian blue analogue hetero-superstructure (PBA-hs) that comprises a Co3[Fe(CN)6]2 cube overcoated with a KCo[Fe(CN)6] shell, followed by eight self-assembled small cubes on vertices. Unlike common directing surfactants, TCA not only acts as a trigger for the fast growth of KCo[Fe(CN)6] on the Co3[Fe(CN)6]2 phase resulting in a PBA-on-PBA hetero-superstructure, but also serves as a flange-like bridge between them. By combining experiments with simulations, a deprotonation-induced electron transfer (DIET) mechanism is proposed for formation of second phase in PBA-hs, differing from thermally and photo-induced electron transfer processes. To prove utility, the calcined PBA-hs exhibits enhanced oxygen evolution reaction performance. This work provides a new method to design of novel CPs for enriching chemistry and material science. This work offers a practical approach to design novel CPs for enriching chemistry and material science.

3.
J Phys Chem Lett ; 15(9): 2428-2435, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38394780

RESUMO

Catalytic performance of single-atom catalysts (SACs) relies fundamentally on the electronic nature and local coordination environment of the active site. Here, based on a machine-learning (ML)-aided density functional theory (DFT) method, we reveal that the intrinsic dipole in Janus materials has a significant impact on the catalytic activity of SACs, using 2D γ-phosphorus carbide (γ-PC) as a model system. Specifically, a local dipole around the active site is a key degree to tune the catalytic activity and can be used as an important descriptor with a high feature importance of 17.1% in predicting the difference of adsorption free energy (ΔGO* - ΔGOH*) to assess the activity of the oxygen evolution reaction. As a result, the catalytic performance of SACs can be tuned by an intrinsic dipole, in stark contrast to those external stimuli strategies previously used. These results suggest that dipole engineering and the revolutionary DFT-ML hybrid scheme are novel approaches for designing high-performance catalysts.

4.
Nanoscale Adv ; 6(2): 638-647, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38235104

RESUMO

The rational design of electrocatalysts with well-designed compositions and structures for the oxygen evolution reaction (OER) is promising and challenging. Herein, we developed a novel strategy - a one-step double-cation etching sedimentation equilibrium strategy - to synthesize amorphous hollow Fe-Co-Ni layered double hydroxide nanocages with an outer surface of vertically interconnected ultrathin nanosheets (Fe-Co-Ni-LDH), which primarily depends on the in situ etching sedimentation equilibrium of the template interface. This unique vertical nanosheet-shell hierarchical nanostructure possesses enhanced charge transfer, increased active sites, and favorable kinetics during electrolysis, resulting in superb electrocatalytic performance for the oxygen evolution reaction (OER). Specifically, the Fe-Co-Ni-LDH nanocages exhibited remarkable OER activity in alkaline electrolytes and achieved a current density of 100 mA cm-2 at a low overpotential of 272 mV with excellent stability. This powerful strategy provides a profound molecular-level insight into the control of the morphology and composition of 2D layered materials.

5.
J Phys Chem Lett ; 14(47): 10537-10544, 2023 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-37972416

RESUMO

Heteroatom incorporation can effectively suppress the phase transition of layered sodium-ion battery cathode, but heteroatom behaviors during operating conditions are not completely understood at the atomic scale. Here, density functional theory calculations are combined with experiments to explore the mitigation behavior of Mg dopant and its mechanisms under operating conditions in P2-Na0.67Ni0.33Mn0.67O2. The void formed by Na extraction will pump some Mg dopants into Na layers from TM layers, and the collective diffusion of more than one Mg ion most likely occurs when the Mg content is relatively high in the TM layer, finally aggregating to form Mg-enrich regions (i.e., Mg segregation) apart from Ni vacancies. The void-pump-effect-induced Mg segregation effectively suppresses the P2-O2 phase transition owing to the stronger Mg-O electrostatic attraction that enhances the integrate of two adjacent oxygen layers and prevents the crack growth by mitigating the lattice volume variation under high-voltage cycling. Our work provides a fundamental understanding of heteroatom mitigation behavior in layered cathodes at the atomic level for next-generation energy storage technologies.

6.
Adv Sci (Weinh) ; 10(32): e2303321, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37814357

RESUMO

The oxygen evolution reaction (OER) activity of transition metal (TM)-based (oxy)hydroxide is dominated by the number and nature of surface active sites, which are generally considered to be TM atoms occupying less than half of surface sites, with most being inactive oxygen atoms. Herein, based on an in situ competing growth strategy of bimetallic ions and OH- ions, a facile one-step method is proposed to modulate oxygen defects in NiFe-layered double hydroxide (NiFe-LDH)/FeOOH heterostructure, which may trigger the single lattice oxygen mechanism (sLOM). Interestingly, by only varying the addition of H2 O2 , one can simultaneously regulate the concentration of oxygen defects, the valence of metal sites, and the ratio of components. The proper oxygen defects promote synergy between the adsorbate evolution mechanism (AEM, metal redox chemistry) and sLOM (oxygen redox chemistry) of OER in NiFe-based (oxy)hydroxide, practically maximizing the use of surface TM and oxygen atoms as active sites. Consequently, the optimal NiFe-LDH/FeOOH heterostructure outperforms the reported non-noble OER catalysts in electrocatalytic activity, with an overpotential of 177 mV to deliver a current density of 20 mA cm-2 and high stability. The novel strategy exemplifies a facile and versatile approach to designing highly active TM-LDH-based OER electrocatalysts for energy and environmental applications.

7.
World J Stem Cells ; 15(5): 476-489, 2023 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-37342222

RESUMO

BACKGROUND: Wound healing impairment is a dysfunction induced by hyperglycemia and its effect on endothelial precursor cells (EPCs) in type 2 diabetes mellitus. There is increasing evidence showing that exosomes (Exos) derived from adipose-derived mesenchymal stem cells (ADSCs) exhibit the potential to improve endothelial cell function along with wound healing. However, the potential therapeutic mechanism by which ADSC Exos contribute to wound healing in diabetic mice remains unclear. AIM: To reveal the potential therapeutic mechanism of ADSC Exos in wound healing in diabetic mice. METHODS: Exos from ADSCs and fibroblasts were used for high-throughput RNA sequencing (RNA-Seq). ADSC-Exo-mediated healing of full-thickness skin wounds in a diabetic mouse model was investigated. We employed EPCs to investigate the therapeutic function of Exos in cell damage and dysfunction caused by high glucose (HG). We utilized a luciferase reporter (LR) assay to analyze interactions among circular RNA astrotactin 1 (circ-Astn1), sirtuin (SIRT) and miR-138-5p. A diabetic mouse model was used to verify the therapeutic effect of circ-Astn1 on Exo-mediated wound healing. RESULTS: High-throughput RNA-Seq analysis showed that circ-Astn1 expression was increased in ADSC Exos compared with Exos from fibroblasts. Exos containing high concentrations of circ-Astn1 had enhanced therapeutic effects in restoring EPC function under HG conditions by promoting SIRT1 expression. Circ-Astn1 expression enhanced SIRT1 expression through miR-138-5p adsorption, which was validated by the LR assay along with bioinformatics analyses. Exos containing high concentrations of circ-Astn1 had better therapeutic effects on wound healing in vivo compared to wild-type ADSC Exos. Immunofluorescence and immunohistochemical investigations suggested that circ-Astn1 enhanced angiopoiesis through Exo treatment of wounded skin as well as by suppressing apoptosis through promotion of SIRT1 and decreased forkhead box O1 expression. CONCLUSION: Circ-Astn1 promotes the therapeutic effect of ADSC-Exos and thus improves wound healing in diabetes via miR-138-5p absorption and SIRT1 upregulation. Based on our data, we advocate targeting the circ-Astn1/miR-138-5p/SIRT1 axis as a potential therapeutic option for the treatment of diabetic ulcers.

8.
Small ; 19(30): e2302906, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37183269

RESUMO

The hollow sandwich core-shell micro-nanomaterials are widely used in materials, chemistry, and medicine, but their fabrication, particularly for transition metal phosphides (TMPs), remains a great challenge. Herein, a general synthesis strategy is presented for binary TMPs hollow sandwich heterostructures with vertically interconnected nanosheets on the inside and outside surfaces of polyhedron FeCoPx /C, demonstrated by a variety of transition metals (including Co, Fe, Cd, Mn, Cu, Cr, and Ni). Density functional theory (DFT) calculation reveals the process and universal mechanism of layered double hydroxide (LDH) growth on Prussian blue analog (PBA) surface in detail for the first time, which provides the theoretical foundations for feasibility and rationality of the synthesis strategy. This unique structure exhibits a vertical nanosheet-shell-vertical nanosheet configuration combining the advantages of sandwich, hollow and vertical heterostructures, effectively achieving their synergistic effect. As a proof-of-concept of their applications, the CoNiPx @FeCoPx /C@CoNiPx hollow sandwich polyhedron architectures (representative samples) show excellent catalytic performance for the oxygen evolution reaction (OER) in alkaline electrolytes. This work provides a general method for constructing hollow-sandwich micro-nanostructures, which provides more ideas and directions for design of micro-nano materials with special geometric topology.

9.
Front Nutr ; 10: 1162031, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37252248

RESUMO

Background and aims: Vitamin C, as an antioxidant, may play a role in the treatment of NAFLD. This research aimed to investigate the association of serum vitamin C levels with the risk of NAFLD and to further examine the causal relationship by Mendelian randomization (MR) method. Methods: The cross-sectional study selected 5,578 participants of the National Health and Nutrition Examination Survey (NHANES), 2005-2006 and 2017-2018. The association of serum vitamin C levels with NAFLD risk was evaluated under a multivariable logistic regression model. A two-sample MR study, using genetic data from large-scale genome-wide association studies (GWAS) of serum vitamin C levels (52,014 individuals) and NAFLD (primary analysis: 1,483 cases /17,781 controls; secondary analysis: 1,908 cases/340,591 controls), was conducted to infer causality between them. The inverse-variance-weighted (IVW) was applied as the main method of MR analysis. A series of sensitivity analyzes were used to evaluate the pleiotropy. Results: In the cross-sectional study, results showed that Tertile 3 group (Tertile 3: ≥1.06 mg/dl) had a significantly lower risk (OR = 0.59, 95% CI: 0.48 ~ 0.74, p < 0.001) of NAFLD than Tertile 1 group (Tertile 1: ≤0.69 mg/dl) after full adjustments. In regard to gender, serum vitamin C was protective against NAFLD in both women (OR = 0.63, 95% CI: 0.49 ~ 0.80, p < 0.001) and men (OR = 0.73, 95% CI: 0.55 ~ 0.97, p = 0.029) but was stronger among women. However, in the IVW of MR analyzes, no causal relationship between serum vitamin C levels and NAFLD risk was observed in the primary analysis (OR = 0.82, 95% CI: 0.47 ~ 1.45, p = 0.502) and secondary analysis (OR = 0.80, 95% CI: 0.53 ~ 1.22, p = 0.308). MR sensitivity analyzes yielded consistent results. Conclusion: Our MR study did not support a causal association between serum vitamin C levels and NAFLD risk. Further studies with greater cases are warranted to confirm our findings.

11.
ACS Nano ; 17(4): 3465-3482, 2023 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-36763083

RESUMO

Photoelectrocatalytic performance of a system is fundamentally determined by the full absorption of sunlight and high utilization of photoexcited carriers, but efficiency of the latter is largely limited by inefficient charge transfer from the absorber to reactive sites. Here, we propose to construct directional charge transfer channels in a monolithically integrated electrode, taking carbon dots/carbon nitride (CCN) nanotubes and FeOOH/FeCo layered double hydroxide (FFC) nanosheets as a representative, to boost the photoassisted overall water splitting performance. Detailed experimental investigations and DFT calculations demonstrate that the interfacial C-O-Fe bonds between CCN and FFC act as charge transfer channels, facilitating the directional migration of the photogenerated carriers between CCN and FFC surfaces. Moreover, the in situ oxidized Fe/Co species by photogenerated holes trigger lattice oxygen activation, realizing the construction of the Fe-Co dual-site as the catalytic center and efficiently lowering the barrier energy for water oxidation. As a result, the CCN@FFC electrode shows multiple functionalities in photoelectrocatalysis: only a low overpotential of 68 mV, 182 mV, and 1.435 V is required to deliver 10 mA cm-2 current densities for the photoassisted HER, OER, and overall water splitting, respectively. This directional charge transfer modulation strategy may facilitate the design of highly active and cost-effective multifunctional catalysts for energy conversion and storage.

12.
J Phys Condens Matter ; 35(7)2022 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-36541486

RESUMO

The novel Bi2O2Se, produced by the oxidation of the layered Bi2Se3, has been considered as one of the most promising candidates for the next-generation electronics owing to its high carrier mobility and air-stability. In this work, by using crystal structure prediction and first-principles calculations, we report the phase transformations from the hexagonal Bi2Se3to the monoclinic Bi2OSe2, and then to the tetragonal Bi2O2Se with the gradual oxidization. Owing to the difference in electronegativity between selenium (Se) and oxygen (O), the oxidation process is accompanied by an increase in bond ionicity. Our results shed light on the phenomena occurring in the interaction between the precursors Bi2Se3and O2and have a potential contribution to the application of optoelectronic devices. The intermediate Bi2OSe2with calculated band gap of 1.01 eV, may be a candidate for photovoltaic application in future.

13.
Kaohsiung J Med Sci ; 38(10): 971-980, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-36149748

RESUMO

Allergic rhinitis (AR) threatens patient survival. CD4+ T cells play key roles in AR progression. Long non-coding RNAs (lncRNAs) are key regulators of cell differentiation. Therefore, we investigated the molecular mechanism of the lncRNA metastasis-associated lung adenocarcinoma transcript 1 (MALAT1) in AR. Expression levels of MALAT1, microRNA (miR)-135b-5p, interleukin-4 (IL-4), and GATA-binding protein 3 (GATA-3) in the nasal mucosa of AR patients were quantified. CD4+ T cells were isolated from the peripheral blood of healthy volunteers and treated with ovalbumin (OVA) and Th2 inducers. After MALAT1 and miR-135b-5p levels changed in CD4+ T cells, the proportion of IL-4-expressing cells and the levels of IL-4 and GATA-3 in OVA-induced CD4+ T cells were determined. Binding relationships among MALAT1, miR-135b-5p, and GATA-3 were predicted and verified. Rescue experiments were performed to confirm the role of the MALAT1/miR-135b-5p/GATA-3 axis in Th2 differentiation of CD4+ T cells. MALAT1, IL-4, and GATA-3 expression was upregulated, whereas miR-135b-5p expression was downregulated, in patients with AR. MALAT1 knockdown or miR-135b-5p overexpression in CD4+ T cells notably decreased the proportion of IL-4-expressing cells and downregulated GATA-3 and IL-4 expression in OVA-induced CD4+ T cells. MALAT1 and GATA-3 exhibited competitive binding toward miR-135b-5p. MALAT1 facilitated CD4+ T cell Th2 differentiation via the miR-135b-5p/GATA-3 axis. MALAT1 facilitated AR development by facilitating CD4+ T cell Th2 differentiation via the miR-135b-5p/GATA-3 axis. This study may provide guidance for clinical treatment of AR.


Assuntos
Fator de Transcrição GATA3/metabolismo , MicroRNAs , RNA Longo não Codificante/genética , Rinite Alérgica , Células Th2 , Diferenciação Celular/genética , Criança , Humanos , Interleucina-4/genética , MicroRNAs/genética , MicroRNAs/metabolismo , Ovalbumina , RNA Longo não Codificante/metabolismo , Rinite Alérgica/genética
14.
Front Microbiol ; 13: 855988, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35401464

RESUMO

Microbial infections cause significant morbidity and mortality in neonates. Metagenomic next-generation sequencing is a hypothesis-free and culture-free test that enables broad identification of pathogens and antimicrobial resistance genes directly from clinical samples within 24 h. In this study, we used mNGS for etiological diagnosis and monitoring the efficacy of antibiotic treatment in a cohort of neonatal patients with severe infections. The median age was 19.5 (3-52) days, median gestational age was 37.96 (31-40+3) weeks, and the median birth weight was 3,261 (1,300-4,300) g. The types of infectious diseases included pneumonia, sepsis, and meningitis. mNGS reported microbial findings in all cases, which led to changes in antibiotic treatment. These included cases of Mycobacterium tuberculosis, Legionella pneumophila, and Bacillus cereus. Eight of ten infants recovered after antibiotic adjustment and showed normal development during follow-up. On the other hand, neurological retardation was seen in two infants with meningitis. mNGS enabled etiological diagnosis and guided antibiotic therapy when all conventional methods failed to discover the culprit. It has the potential to cut down the overall cost and burden of disease management in neonatal infections.

15.
Sci Rep ; 11(1): 21871, 2021 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-34750490

RESUMO

Derived from the most abundant natural polymer, cellulose nanocrystal materials have attracted attention in recent decades due to their chemical and mechanical properties. However, still unclear is the influence of different exposed facets of the cellulose nanocrystals on the physicochemical properties. Herein, we first designed cellulose II nanocrystals with different exposed facets, the hydroxymethyl conformations distribution, hydrogen bond (HB) analysis, as well as the relative structural stability of these models (including crystal facets {A, B, O} and Type-A models vary in size) are theoretically investigated. The results reveal that the HB network of terminal anhydroglucose depends on the adjacent chain's contact sites in nanocrystals exposed with different facets. Compared to nanocrystals exposed with inclined facet, these exposed with flat facet tend to be the most stable. Therefore, the strategy of tuning exposed crystal facets will guide the design of novel cellulose nanocrystals with various physicochemical properties.

16.
J Phys Chem A ; 125(14): 2905-2912, 2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33822612

RESUMO

A recently synthesized novel molecule (named CAT-1) exhibits intriguing near-infrared (NIR) thermally activated delayed fluorescence (TADF) close to 1000 nm wavelength; however, the mechanism behind these intrinsic properties is not fully understood. Herein, we unravel that the fluorescence emission spectrum with a broad wavelength range (770-950 nm) of CAT-1 is primarily induced by hydrogen bond steric hindrance based on density functional theory and Marcus theory. It is found that the hydrogen bond steric hindrance plays a critical role in inhibiting the twist of the configuration of different excited states, which leads to the minor driving force for fast electron trapping between the excited states, as well as small internal reorganization energy caused by less changed geometric configuration. Furthermore, such steric hindrance will cause a more distorted plane, resulting in a less favorable electron delocalization. A faster reverse intersystem crossing (RISC) rate is then obtained due to the nearly unchanged conformation between excited states caused by steric hindrance, although the spin-orbit coupling is small. Consequently, the NIR TADF with a longer wavelength can be emitted in CAT-1. This work shows that the hydrogen bond steric hindrance can fine-tune the electronic interactions of the donor and acceptor units to control the TADF.

17.
ACS Nano ; 15(3): 4481-4489, 2021 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-33656862

RESUMO

As a two-dimensional semiconductor with many physical properties, including, notably, layer-controlled electronic bandgap and coupled spin-valley degree of freedom, monolayer MoSe2 is a strong candidate material for next-generation opto- and valley-electronic devices. However, due to substrate effects such as lattice mismatch and dielectric screening, preserving the monolayer's intrinsic properties remains challenging. This issue is generally significant for metallic substrates whose active surfaces are commonly utilized to achieve direct chemical or physical vapor growth of the monolayer films. Here, we demonstrate high-temperature-annealed Au foil with well-defined (100) facets as a weakly interacting substrate for atmospheric pressure chemical vapor deposition of highly crystalline monolayer MoSe2. Low-temperature scanning tunneling microscopy/spectroscopy measurements reveal a honeycomb structure of MoSe2 with a quasi-particle bandgap of 1.96 eV, a value comparable with other weakly interacting systems such as MoSe2/graphite. Density functional theory calculations indicate that the Au(100) surface exhibits the preferred energetics to electronically decouple from MoSe2, compared with the (110) and (111) crystal planes. This weak coupling is critical for the easy transfer of monolayers to another host substrate. Our study demonstrates a practical means to produce high-quality monolayers of transition-metal dichalcogenides, viable for both fundamental and application studies.

18.
Nanoscale Res Lett ; 15(1): 180, 2020 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-32955632

RESUMO

Two-dimensional (2D) transition metal dichalcogenides with intrinsically passivated surfaces are promising candidates for ultrathin optoelectronic devices that their performance is strongly affected by the contact with the metallic electrodes. Herein, first-principle calculations are used to construct and investigate the electronic and interfacial properties of 2D MoTe2 in contact with a graphene electrode by taking full advantage of them. The obtained results reveal that the electronic properties of graphene and MoTe2 layers are well preserved in heterostructures due to the weak van der Waals interlayer interaction, and the Fermi level moves toward the conduction band minimum of MoTe2 layer thus forming an n type Schottky contact at the interface. More interestingly, the Schottky barrier height and contact types in the graphene-MoTe2 heterostructure can be effectively tuned by biaxial strain and external electric field, which can transform the heterostructure from an n type Schottky contact to a p type one or to Ohmic contact. This work provides a deeper insight look for tuning the contact types and effective strategies to design high performance MoTe2-based Schottky electronic nanodevices.

19.
Nanoscale ; 12(10): 6037-6046, 2020 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-32129406

RESUMO

Efficient spatial charge separation and transfer that are critical factors for solar energy conversion primarily depend on the energetic alignment of the band edges at interfaces in heterojunctions. Herein, we first report that constructing a 0D/0D type-II(T-II)/T-II heterojunction is an effective strategy to ingeniously achieve long-range charge separation by taking a ternary heterojunction of TiO2 and graphitic carbon nitride (g-C3N4) as a proof-of-concept. Incorporating g-C3N4 quantum dots (QCN), as the third component, into the commercial P25 composed of anatase (a-TiO2) and rutile (r-TiO2) can be realized via simply mixing the commercially available Degussa P25 and QCN solution followed by heat treatment. The strong coupling and matching band structures among a-TiO2, r-TiO2 and QCN result in the construction of novel T-II/T-II heterojunctions, which would promote the spatial separation and transfer of photogenerated electrons and holes. Moreover, QCN plays a key role in reinforcing light absorption. Particularly, the unique 0D/0D architecture possesses the advantages of abundant active sites for the photocatalytic reaction. As a result, the optimized QCN/a-TiO2/r-TiO2 heterojunctions exhibit enhanced photocatalytic H2 and O2 evolution, especially the hydrogen evolution rate (49.3 µmol h-1) is 11.7 times that of bare P25 under visible light irradiation, and sufficient catalytic stability as evidenced by the recycling experiments. The remarkably enhanced photocatalytic activity can be attributed to the synergistic effects of the energy level alignment at interfaces, the dimensionality and component of the heterojunctions. This work provides a stepping stone towards the design of novel heterojunctions for photocatalytic water splitting.

20.
Adv Mater ; 32(11): e1906015, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-32027058

RESUMO

Developing low-cost, highly efficient, and durable electrocatalysts for oxygen evolution reaction (OER) is essential for the practical application of electrochemical water splitting. Herein, it is discovered that organic small molecule (hexabromobenzene, HBB) can activate commercial transition metal (Ni, Fe, and NiFe) foam by directly evolving metal nanomeshes embedded in graphene-like films (M-NM@G) through a facile Br-induced solid-phase migration process. Systematic investigations indicate that HBB can conformally generate graphene-like network on bulk metal foam substrate via the cleavage of CBr bonds and the formation of CC linkage. Simultaneously, the cleaved CBr fragments can efficiently extract metal atoms from bulk substrate, in situ producing transition metal nanomeshes embedded in the graphene-like films. As a result, such functional nanostructure can serve as an efficient OER electrocatalyst with a low overpotential and excellent long-term stability. Specifically, the overpotential at 100 mA cm-2 is only 208 mV for NiFe-NM@G, ranking the top-tier OER electrocatalysts. This work demonstrates an intriguing general strategy for directly transforming bulk transition metals into nanostructured functional electrocatalysts via the interaction with organic small molecules, opening up opportunities for bridging the application of organic small molecules in energy technologies.

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