Production of clean hydrogen energy from water splitting is vital for the future fuel industry, and nanocomposites have emerged as effective catalysts for the hydrogen evolution reaction (HER). In this study, Ru-CoO@SNG nanocomposites are prepared by controlled pyrolysis where Ru-CoO heterostructured nanoparticles are supported on nitrogen and sulfur codoped graphene oxide nanosheets. With a large surface area, the obtained composites exhibit a remarkable electrocatalytic activity toward HER in 1.0 M KOH with an overpotential of only −90 mV to reach the current density of 10 mA cm−2 , in comparison to −60 mV for commercial Pt/C benchmark, along with high stability. Mechanistically, codoping of sulfur and nitrogen facilitates the dispersion of the nanoparticles, and the formation of Ru-CoO heterostructures increases the active site density, reduces the electron-transfer kinetics and boosts the catalytic performance. Results from this study highlight the unique potential of structural engineering in enhancing the electrocatalytic performance of heterostructured nanocomposites.
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Heterostructured Bi–Cu2S nanocrystals for efficient CO2 electroreduction to formate
The electrochemical CO2 reduction reaction (ECO2RR) driven by renewable electricity holds promise to store intermittent energy in chemical bonds, while producing value-added chemicals and fuels sustainably. Unfortunately, it remains a grand challenge to simultaneously achieve a high faradaic efficiency (FE), a low overpotential, and a high current density of the ECO2RR. Herein, we report the synthesis of heterostructured Bi–Cu2S nanocrystals via a one-pot solution-phase method. The epitaxial growth of Cu2S on Bi leads to abundant interfacial sites and the resultant heterostructured Bi–Cu2S nanocrystals enable highly efficient ECO2RR with a largely reduced overpotential (240 mV lower than that of Bi), a near-unity FE (>98%) for formate production, and a high partial current density (2.4- and 5.2-fold higher JHCOO− than Cu2S and Bi at −1.0 V vs. reversible hydrogen electrode, RHE). Density functional theory (DFT) calculations show that the electron transfer from Bi to Cu2S at the interface leads to the preferential stabilization of the formate-evolution intermediate (*OCHO).
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- NSF-PAR ID:
- 10322776
- Date Published:
- Journal Name:
- Nanoscale Horizons
- ISSN:
- 2055-6756
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract A crucial step toward clean hydrogen (H2) energy production through water electrolysis is to develop high‐stability catalysts, which can be reliably used at high current densities for a long time. So far, platinum group metals (PGM) and their oxides, for example, Pt and iridium oxide (IrO2) have been well‐regarded as the criterion for hydrogen and oxygen evolution reactions (HER and OER) electrocatalysts. However, the PGM catalysts usually undergo severe performance decay during the long‐term operation. Herein, the in situ growth of iron phosphosulfate (Fe2P2S6) nanocrystals (NCs) catalysts on carbon paper synthesized by combing chemical vapor deposition with solvent‐thermal treatment is reported to show competitive performance and stability as compared to the state‐of‐the‐art PGM catalysts in a real water electrolyzer. A current density of 370 mA cm−2is achieved at 1.8 V when using Fe2P2S6NCs as bifunctional catalysts in an anion exchange membrane water electrolyzer. The Fe2P2S6NCs also show much better stability than the Pt‐IrO2catalysts at 300 mA cm−2for a continuous 24 h test. The surface generated FeOOH on Fe2P2S6is the real active site for OER. These results indicate that the Fe2P2S6NCs potentially can be used to replace PGM catalysts for practical water electrolyzers.
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null (Ed.)Lead-free perovskites and their analogues have been extensively studied as a class of next-generation luminescent and optoelectronic materials. Herein, we report the synthesis of new colloidal Cs 4 M( ii )Bi 2 Cl 12 (M( ii ) = Cd, Mn) nanocrystals (NCs) with unique luminescence properties. The obtained Cs 4 M( ii )Bi 2 Cl 12 NCs show a layered double perovskite (LDP) crystal structure with good particle stability. Density functional theory calculations show that both samples exhibit a wide, direct bandgap feature. Remarkably, the strong Mn–Mn coupling effect of the Cs 4 M( ii )Bi 2 Cl 12 NCs results in an ultra-short Mn photoluminescence (PL) decay lifetime of around 10 μs, around two orders of magnitude faster than commonly observed Mn 2+ dopant emission in NCs. Diluting the Mn 2+ ion concentration through forming Cs 4 (Cd 1−x Mn x )Bi 2 Cl 12 (0 < x < 1) alloyed LDP NCs leads to prolonged PL lifetimes and enhanced PL quantum yields. Our study provides the first synthetic example of Bi-based LDP colloidal NCs with potential for serving as a new category of stable lead-free perovskite-type materials for various applications.more » « less
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Bimagnetic nanoparticles show promise for applications in energy efficient magnetic storage media and magnetic device applications. The magnetic properties, including the exchange bias of nanostructured materials can be tuned by variation of the size, composition, and morphology of the core vs overlayer of the nanoparticles (NPs). The purpose of this study is to investigate the optimal synthesis routes, structure and magnetic properties of novel CoO/NiFe 2 O 4 heterostructured nanocrystals (HNCs). In this work, we aim to examine how the size impacts the exchange bias, coercivity and other magnetic properties of the CoO/NiFe 2 O 4 HNCs. The nanoparticles with sizes ranging from 10 nm to 24 nm were formed by synthesis of an antiferromagnetic (AFM) CoO core and deposition of a ferrimagnetic (FiM) NiFe 2 O 4 overlayer. A highly crystalline magnetic phase is more likely to occur when the morphology of the core-overgrowth is present, which enhances the coupling at the AFM-FiM interface. The CoO core NPs are prepared using thermal decomposition of Co(OH) 2 at 600 °C for 2 hours in a pure argon atmosphere, whereas the HNCs are obtained first using thermal evaporation followed by hydrothermal synthesis. The structural and morphological characterization made using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and scanning electron microscopy (SEM) techniques verifies that the HNCs are comprised of a CoO core and a NiFe 2 O 4 overgrowth phase. Rietveld refinement of the XRD data shows that the CoO core has the rocksalt (Fd3 m) crystal structure and the NiFe 2 O 4 overgrowth has the spinel (C12/m1) crystal structure. SEM-EDS data indicates the presence and uniform distribution of Co, Ni and Fe in the HNCs. The results from PPMS magnetization measurements of the CoO/NiFe 2 O 4 HNCs are discussed herein.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1NH00661D
