The
rational design and controllable synthesis of hollow nanoparticles
with both a mesoporous shell and an asymmetric architecture are crucially
desired yet still significant challenges. In this work, a kinetics-controlled
interfacial super-assembly strategy is developed, which is capable
of preparing asymmetric porous and hollow carbon (APHC) nanoparticles
through the precise regulation of polymerization and assembly rates
of two kinds of precursors. In this method, Janus resin and silica
hybrid (RSH) nanoparticles are first fabricated through the kinetics-controlled
competitive nucleation and assembly of two precursors. Specifically,
silica nanoparticles are initially formed, and the resin nanoparticles
are subsequently formed on one side of the silica nanoparticles, followed
by the co-assembly of silica and resin on the other side of the silica
nanoparticles. The APHC nanoparticles are finally obtained via high-temperature
carbonization of RSH nanoparticles and elimination of silica. The
erratic asymmetrical, hierarchical porous and hollow structure and
excellent photothermal performance under 980 nm near-infrared (NIR)
light endow the APHC nanoparticles with the ability to serve as fuel-free
nanomotors with NIR-light-driven propulsion. Upon illumination by
NIR light, the photothermal effect of the APHC shell causes both self-thermophoresis
and jet driving forces, which propel the APHC nanomotor. Furthermore,
with the assistance of phase change materials, such APHC nanoparticles
can be employed as smart vehicles that can achieve on-demand release
of drugs with a 980 nm NIR laser. As a proof of concept, we apply
this APHC-based therapeutic system in cancer treatment, which shows
improved anticancer performance due to the synergy of photothermal
therapy and chemotherapy. In brief, this kinetics-controlled approach
may put forward new insight into the design and synthesis of functional
materials with unique structures, properties, and applications by
adjusting the assembly rates of multiple precursors in a reaction
system.
Alloy/perovskite composites prepared by exsolution of
Fe-based
perovskite have attracted wide attention due to their embedded and
well-anchored structure, which have broad applications in heterogeneous
catalysis and energy conversion. Herein, we use Co-doped lanthanum
ferrite as a model to study the effect of doping on the B-site exsolution
of Fe-based perovskite. CoFe alloy can be exsolved from La0.9Fe0.9Co0.1O3 (LFCO) after heat treatment
at 500 °C in a reduced atmosphere, whereas Fe will not be exsolved
from La0.9FeO3 (LFO). Density functional theory
calculations revealed that the stability of LFCO decreased after Co
is doped into the lanthanum ferrite perovskite lattice and the formation
energy of the Co–Fe bond on the surface of LFCO is lower than
that of Fe–Fe in LFO, which promises an easier exsolution of
CoFe alloy than the pristine Fe cluster. In addition, owing to the
strong interaction and charge transfer between the exsolved CoFe alloy
and parent perovskite, as well as the longer Fe–O bond after
exsolution, the exsolved composite can act as an excellent bifunctional
electrocatalyst for oxygen evolution and oxygen reduction reactions.
Our work not only reveals the mechanism of the alloy exsolution in
Fe-based perovskites but also provides a potential route to prepare
the highly efficient electrocatalysts.
The
exsolution of noble metal nanoparticles (NPs) from perovskite
usually requires high doping ratio of noble metal. Herein, we constructed
a RuO2/LFRO composite by the exsolution of a low Ru-substituted
A-site deficient perovskite, La0.9Fe0.92Ru0.08O3 (LFRO). In this process, pure Ru NPs are
in situ exsolved from LFRO via a relatively low temperature heat treatment
in 5% H2/Ar. Then the exsolved Ru NPs were oxidized to
RuO2 for oxygen evolution reaction (OER) applications.
The RuO2/LFRO composite achieved a high OER performance
compared with the pristine LFRO, which is mainly originated from the
generation of electrochemically active RuO2 NPs and the
improvement of conductivity. In addition, the exsolution is a reversible
process that the exsolved Ru NPs can disappear into the perovskite
lattice at 550 °C in air. Our work thereof demonstrates an effective
strategy to minimize the dosage of precious metals for catalytic applications
in different fields.
Metal−air batteries have attracted great attention because of their high energy density merits, among which zinc−air batteries (ZABs) are of great interest owing to their high energy density, intrinsic safety, and low cost. However, sluggish kinetics of the electrochemical oxygen evolution reactions and oxygen reduction reactions (OER and ORR) greatly hinder the development of ZABs. [5,6] Preparing a low-cost electrocatalyst with low overpotential and high stability is thereof a key issue. Effective synthesis methods are appealing to obtain robust catalysts. [7][8][9] Previous reports show that modifying the surface or bulk of materials by constructing composites, such as heterogeneous phase constructing, vacancy constructing, and interfacial engineering, can largely improve the performance of catalysts. [10][11][12][13] With regard to structural regulation, disrupting long-range order by constructing composite structures facilitates to obtain unexpected catalytic properties due to the synergistic coupling effect. [4,14] These methods can merely improve the performance of specific catalytic reactions, however, the method universality remains being improved.Surface modification and reconstruction are interesting topics from a viewpoint of catalysis, and many challenges Constructing composite structures is an essential approach for obtaining multiple functionalities in a single entity. Available synthesis methods of the composites need to be urgently exploited; especially in situ construction. Here, a NiS/NiFe 2 O 4 composite through a local metal−S coordination at the interface is reported, which is derived from phase reconstruction in the highly defective matrix. X-ray absorption fine structure confirms that long-range order is broken via the local metal−S coordination and, by using electron energy loss spectroscopy, the introduction of NiS/NiFe 2 O 4 interfaces during the irradiation of plasma energy is identified. Density functional theory (DFT) calculations reveal that in situ phase reconfiguration is crucial for synergistically reducing energetic barriers and accelerating reaction kinetics toward catalyzing the oxygen evolution reaction (OER). As a result; it leads to an overpotential of 230 mV @10 mA cm −2 for the OER and a half-wave potential of 0.81 V for the oxygen reduction reaction (ORR); as well as an excellent zinc−air battery (ZAB) performance with a power density of 148.5 mW cm −2 . This work provides a new compositing strategy in terms of fast phase reconstruction of bifunctional catalysts.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202110172.
The ethanol oxidation reaction (EOR), the anode reaction of direct ethanol fuel cells, suffers from the sluggish oxidation kinetics and its low selectivity toward complete oxidation to CO2. The key...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.