Fabrication Of Nanocrystals Research Articles

Tuning Perovskite Nanocrystal Synthesis via Amphiphilic Block Copolymer Templates and Solvent Interactions.

Amphiphilic block copolymer (a-BCP) micelles offer morphological diversity and dimensional tunability, making them suitable for the fabrication of perovskite nanocrystals. However, precise control over the nucleation and growth of perovskite nanocrystals using a-BCP colloidal templates remains underexplored. This study investigates the effects of toluene, methanol, and polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) on the formation of cesium lead bromide (CsPbBr3) nanocrystals. The process involves four stages: (i) PS-b-P2VP micellization, (ii) PbBr2 complexation, (iii) coordination interaction with P2VP, and (iv) burst nucleation of CsPbBr3 nanocrystals. Toluene, a good solvent for PS but a nonsolvent for P2VP, PbBr2, and CsBr, facilitates the formation of PS-b-P2VP spherical micelles. Adding PbBr2 to these micelles in toluene results in multiple emulsion, dispersing PbBr2 microstructures (microemulsion) and forming [PbBr3]- complexes encapsulated by the micelles (nanoemulsion). Prolonged stirring enhances this nanoemulsion. CsBr, insoluble in toluene, must be dissolved in methanol before being mixed with micelle-encapsulated complexes, promoting quick crystal nucleation. However, excess methanol weakens micellization, leading to the formation of fused micelles and irregular nanocrystals. At a high methanol content, [PbBr4]2- complexes also form, driving CsPbBr3 to CsPb2Br5 transformation via Ostwald ripening, resulting in large CsPb2Br5 microcrystals that precipitate due to gravitational forces overcoming Brownian motion, destabilizing their dispersion in the solution.

Palladium nanocrystals immobilized on boron and nitrogen codoped mesoporous carbon spheres as efficient methanol oxidation electrocatalysts

The development of cost-effective and high-performance electrocatalysts is crucial for the widespread application of direct methanol fuel cell. Herein, a convenient and robust method is developed to the controllable fabrication of Pd nanocrystals in situ immobilized on boron and nitrogen codoped mesoporous carbon spheres (Pd/BNMCS) as anode catalysts for the methanol oxidation reaction. The as-derived Pd/BNMCS hybrids are equipped with a series of useful structural features, such as large specific surface area, abundant mesoporous channels, presence of plentiful B and N atoms, well-dispersive Pd nanoparticles, and good electrical conductivity. As a consequence, the optimized Pd/BNMCS catalyst demonstrates superior electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area, high mass/specific activities, and reliable long-term stability, which are significantly better than those of traditional carbon black and undoped mesoporous carbon sphere supported Pd catalysts. This study highlights the potential of heteroatom codoped mesoporous carbon matrixes in the construction of advanced noble metal electrocatalysts for practical fuel cell applications.

Synthesis of Cs3Cu2I5 Nanocrystals in a Continuous Flow System.

Achieving the goal of generating all of the world's energy via renewable sources and significantly reducing the energy usage will require the development of novel, abundant, nontoxic energy conversion materials. Here, a cost-efficient and scalable continuous flow synthesis of Cs3Cu2I5 nanocrystals is developed as a basis for the rapid advancement of novel nanomaterials. Ideal precursor solutions are obtained through a novel batch synthesis, whose product served as a benchmark for the subsequent flow synthesis. Realizing this setup enabled a reproducible fabrication of Cs3Cu2I5 nanocrystals. The effect of volumetric flow rate and temperature on the final product's morphology and optical properties are determined, obtaining 21% quantum yield with the optimal configuration. Consequently, the size and morphology of the nanocrystals can be tuned with far more precision and in a much broader range than previously achievable. The flow setup is readily applicable to other relevant nanomaterials. It should enable a rapid determination of a material's potential and subsequently optimize its desired properties for renewable energy generation or efficient optoelectronics.

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Flower-like Al2O3 materials were successfully incorporated by TS-1 nanocrystals to synthesize Flower-like TS-1-Al2O3 (FTA) micro-mesoporous composite by a facile nano self-assembly method. FTA supported NiMo bimetallic catalysts (NiMo/FTA) were further constructed and applied to the hydrodesulfurization (HDS) reactions for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). FTA composites were constructed from flower-like pore structures stacked with nanosheets, which are conducive to the even load and dispersion of active species and the diffusion of macromolecular sulfur-containing compounds with relatively low resistance. The fabrication of TS-1 nanocrystals effectively enhanced the acidic sites, regulated the metal-support interaction, which could increase the stacking layer of MoS2 slabs, and producing more NiMoS-II type active phase. NiMo/FTA-10 presented the excellent HDS conversion of DBT (99.3 %) and 4,6-DMDBT (93.2 %) at 10 h−1, the highest reaction rate constant (2.6 × 10-7 mol g−1 s−1) and turnover frequency values (6.7 × 10-4 s−1) for 4,6-DMDBT HDS reaction. Compared to the direct desulfurization route (DDS), hydrogenation route (HYD) and isomerization route (ISO) can effectively eliminate the steric hindrance of 4,6-DMDBT, which is more conducive to the HDS reaction.

Lipid-coated nanocrystals of paclitaxel as dry powder for inhalation: Characterization, in-vitro performance, and pharmacokinetic assessment

BackgroundNanocrystals can be produced as a dry powder for inhalation (DPIs) to deliver high doses of drug to the lungs, owing to their high payload and stability to the shear stress of aerosolization force. Furthermore, lipid-coated nanocrystals can be formulated to improve the drug accumulation and retention in lung. ObjectiveThe present work involved the fabrication of paclitaxel nanocrystals using hydrophilic marine biopolymer fucoidan as a stabilizer. Thereafter, fabricated nanocrystals (FPNC) were surface-modified with phospholipid to give lipid-coated nanocrystals (Lipo-NCs). MethodsThe nanocrystals were fabricated by antisolvent crystallization followed by the probe sonication. The lipid coating was achieved by thin film hydration followed ultrasonic dispersion technique. Prepared nanocrystals were lyophilized to obtain a dry powder of FPNC and Lipo-NCs, used later for physicochemical, microscopic, and spectroscopic characterization to confirm the successful formation of desired nanocrystals. In-vitro and in-vivo investigations were also conducted to determine the role of nanocrystal powder in pulmonary drug delivery. ResultsLipo-NCs exhibited slower drug release, excellent flow properties, good aerosolization performance, higher drug distribution, and prolonged retention in the lungs compared to FPNC and pure PTX. ConclusionLipid-coated nanocrystals can be a novel formulation for the maximum localization of drugs in the lungs, thereby enhancing therapeutic effects and avoiding systemic side effects in lung cancer therapy.

Exploring the potential of powder-to-film processing for proof-of-concept BaZrS3 perovskite solar cells

Lead-free chalcogenide perovskites, such as BaZrS3, manifest as strong candidates to replace toxic metals-containing halide perovskites in optoelectronic applications, but the formation of high-quality films for photovoltaic applications remains a major challenge for now, since very high temperatures are needed to fully crystalize the compound. To circumvent this issue, liquid-phase synthesis, through direct fabrication of perovskite nanocrystals dispersed in an organic solvent or a conversion of a pre-crystalline powder to an ink, has been suggested as a viable strategy for low-temperature processing. However, both cases result in films which cannot be used in the fabrication of solar cells. Herein, in this work, we adopt the latter approach, and convert BaZrS3 particles, from solid-state synthesis to a stable colloidal dispersion in a Ν-Methyl-2-pyrrolidone (NMP)-oleylamine (OA) mixture. We report a detailed identification of the structural changes of this transformation with a large range of crystallographic, spectroscopic and microscopic techniques. Then, we evaluate the feasibility of the process for the fabrication of films. BaZrS3 infiltrated in mesoporous TiO2/FTO transparent glass substrates were used as photolectrodes in solar cells and proof-of concept devices were constructed in conjunction with I3-/I- redox electrolyte for the first time in literature, reaching a mean PCE of 0.11% and a FF of 61%. We believe that this work will pave the way towards the systematic use of BaZrS3 (or other similar chalcogenide perovskites) in solar cells and other relevant optoelectronic devices.

Fabrication of Nanocrystals for Enhanced Distribution of a Fatty Acid Synthase Inhibitor (Orlistat) as a Promising Method to Relieve Solid Ehrlich Carcinoma-Induced Hepatic Damage in Mice.

Orlistat (ORL) is an effective irreversible inhibitor of the lipase enzyme, and it possesses anticancer effects and limited aqueous solubility. This study was designed to improve the aqueous solubility, oral absorption, and tissue distribution of ORL via the formulation of nanocrystals (NCs). ORL-NC was prepared using the liquid antisolvent precipitation method (bottom-up technology), and it demonstrated significantly improved solubility compared with that of the blank crystals (ORL-BCs) and untreated ORL powder. The biodistribution and relative bioavailability of ORL-NC were investigated via the radiolabeling technique using Technetium-99m (99mTc). Female Swiss albino mice were used to examine the antitumor activity of ORL-NC against solid Ehrlich carcinoma (SEC)-induced hepatic damage in mice. The prepared NCs improved ORL's solubility, bioavailability, and tissue distribution, with evidence of 258.70% relative bioavailability. In the in vivo study, the ORL-NC treatment caused a reduction in all tested liver functions (total and direct bilirubin, AST, ALT, and ALP) and improved modifications in liver sections that were marked using hematoxylin and eosin staining (H&E) and immunohistochemical staining (Ki-67 and ER-α) compared with untreated SEC mice. The developed ORL-NC could be considered a promising formulation approach to enhance the oral absorption tissue distribution of ORL and suppress the liver damage caused by SEC.

Green synthesis of ZnO nano-crystals using Chenopodium album L. Leaf extract, their characterizations and antibacterial activities

We present an effective, simple and eco-friendly method for the green synthesis of ZnO nano-crystals. An aqueous extract of Chenopodium album leaf was used as a biological reducing agent for the fabrication of ZnO nano-crystals from the zinc sulphate heptahydrate. The as-prepared and annealed powder samples were characterized using advanced techniques. The results confirmed the presence of ZnO crystals with a broad size distribution, whose crystallinity was noticed to improve substantially after the annealing. Further, in antibacterial activity test of ZnO nano-crystals performed on Escherichia coli and Staphylococcus aureus microorganisms, inhibitory effect was found to increase with concentration. Compared to Gram-positive bacteria, ZnO nano-crystals showed more resistance to Gram-negative bacteria. This green synthesis route of ZnO nano-crystals is novel and aims to reduce the use of toxic chemicals in fabricating the nanoparticles of functional oxides, which have a wide range of potential applications in general and biomedical science, in particular.

Fabrication of lipase immobilized-carboxylated cellulose nanocrystals as biocatalyst for enzymatic hydrolysis of palm oil and its kinetical study

This research focuses on the production of free fatty acids (FFA), one of the essential components in the oleochemical industry, through the enzymatic hydrolysis process of palm oil at low temperature and pressure using cellulose nanocrystals (CNCs) as lipase immobilization support. Furthermore, the kinetic behavior of this hydrolysis reaction with the presence of lipase immobilized-CNCs (lipase@CNCs) was studied to find the optimum condition for designing the reactor. According to FTIR and TEM analyses, CNCs were successful in immobilizing lipases, as ascertained by the appearance of amide peaks from the formation of bonds between CNCs and lipases and the thickening of the surface of the CNC morphology after immobilization. As a result, the optimum immobilization conditions were obtained at a lipase concentration of 1.5 mg/mL, an immobilization time of 2 h, and the CNCs/EDC ratio of 1:3. Moreover, the Michaelis-Menten model with the inhibition product fitted with the experiment and lipase@CNCs has the highest Vmax value at a temperature of 40 °C of 15.53 mM/h with a KM of 99.80 mM and an Ea of 41.07 kJ/mol. The simulation results show that the semi-batch reactor can achieve a higher conversion at the beginning of the reaction with a conversion of 28%. Therefore, using lipase@CNCs in hydrolysis processes is expected to be one of the strategies that can overcome the limitations associated with existing methods in terms of high energy consumption.

Nucleation and Growth of Nanocrystals Investigated by In Situ Transmission Electron Microscopy.

Nanocrystals play a key role in the modern energy, catalysis, semiconductor, and biology industries due to their unique structures and performances. However, controllable fabrication of ideal nanocrystals with the desired structures and properties is still challenging, which needs a deep understanding of their nucleation and growth process. Here, the research on nucleation and growth of nanocrystals studied by in situ transmission electron microscopy (TEM) is reviewed, mainly focusing on the atomic migration dynamics, interface evolution, and structure transformation. In addition, the challenges in the study of nanocrystal growth by TEM are discussed and the perspective on the future development of advanced in situ TEM techniques is provided. It is hoped that the review can give a deep insight into the nanocrystal nucleation and growth process, and further contribute to the rational design and precise fabrication of high-performance functional nanocrystals.

Self-Standing Pd-Based Nanostructures for Electrocatalytic CO Oxidation: Do Nanocatalyst Shape and Electrolyte pH Matter?

Tailoring the shape of Pd nanocrystals is one of the main ways to enhance catalytic activity; however, the effect of shapes and electrolyte pH on carbon monoxide oxidation (COOxid) is not highlighted enough. This article presents the controlled fabrication of Pd nanocrystals in different morphologies, including Pd nanosponge via the ice-cooling reduction of the Pd precursor using NaBH4 solution and Pd nanocube via ascorbic acid reduction at 25 °C. Both Pd nanosponge and Pd nanocube are self-standing and have a high surface area, uniform distribution, and clean surface. The electrocatalytic CO oxidation activity and durability of the Pd nanocube were significantly superior to those of Pd nanosponge and commercial Pd/C in only acidic (H2SO4) medium and the best among the three media, due to the multiple adsorption active sites, uniform distribution, and high surface area of the nanocube structure. However, Pd nanosponge had enhanced COOxid activity and stability in both alkaline (KOH) and neutral (NaHCO3) electrolytes than Pd nanocube and Pd/C, attributable to its low Pd-Pd interatomic distance and cleaner surface. The self-standing Pd nanosponge and Pd nanocube were more active than Pd/C in all electrolytes. Mainly, the COOxid current density of Pd nanocube in H2SO4 (5.92 mA/cm2) was nearly 3.6 times that in KOH (1.63 mA/cm2) and 10.3 times that in NaHCO3 (0.578 mA/cm2), owing to the greater charge mobility and better electrolyte-electrode interaction, as evidenced by electrochemical impedance spectroscopy (EIS) analysis. Notably, this study confirmed that acidic electrolytes and Pd nanocube are highly preferred for promoting COOxid and may open new avenues for precluding CO poisoning in alcohol-based fuel cells.

Ultrafast Laser Plasmonic Fabrication of Nanocrystals by Molecule Modulation for Photoresponse Multifunctional Structures.

Nanotechnology has attracted wide research attention in constructing functional devices, including integrated circuits, transparent electrodes, and flexible actuators. Bottom-up fabrication is an important approach for functional structure manufacture, however, the controllable fabrication of complex architectures for practical applications has long been a challenge. Here, a novel strategy of laser plasmonic fabrication based on glue molecule modulation is proposed that can assemble metal nanocrystals into interconnected pattern networks. The plasmonic response of nanocrystals is adjustable with molecule modulation, which is a benefit for the effective formation of laser-induced localized oscillating electrons. The further decomposition of molecules and the movement of nanocrystal surface atoms can achieve the coalescence of assembled nanocrystals. It demonstrates that complex architectures can be controllably constructed by molecule level modulation. Through molecule-assisted laser plasmonic fabrication, the functional nanocrystals with enhanced photothermal capacity can be used for information encryption and soft machinery. This work expands the knowledge of bottom-up fabrication and provides a method for designing functional nanocrystals for a wide range of applications.

Microemulsion-Based Fabrication of Organic Nanocrystals for Persistent Phosphorescence Bioimaging

Persistent phosphorescence eliminates the need for light excitation and thus avoids the issue of autofluorescence, holding great promise in various fields. To achieve bright phosphorescence emission, many methods were developed to confine most organic persistent phosphorescent materials in a rigid environment aiming to quench nonradiative relaxation pathways; among them, the nanocrystal method is a good candidate which can rigidify the molecules as well as offer the desirable water dispersity and size for further bioapplications. However, the current efficient preparation of phosphorescent nanocrystals still remains challenging. This study reports an efficient microemulsion-based method for the fabrication of phosphorescent nanocrystals with a desired diameter in the nanosize range (below 200 nm), a high phosphorescence quantum yield of about 6.5%, and ultralong persistent phosphorescence to the timescale after the removal of the external light source, making it easy for the commercial imaging system to detect, which is suitable for practical bioimaging. Furthermore, the synthesized nanocrystals with biocompatibility were utilized directly for in vitro imaging, showing effective cellular uptake and bright phosphorescence emission, which provides a reasonable strategy to develop a phosphorescent nanocrystal for application.

Formulation and Optimization of Repaglinide Nanoparticles Using Microfluidics for Enhanced Bioavailability and Management of Diabetes

The technologies for fabrication of nanocrystals have an immense potential to improve solubility of a variety of the poor water-soluble drugs with subsequent enhanced bioavailability. Repaglinide (Rp) is an antihyperglycemic drug having low bioavailability due to its extensive first-pass metabolism. Microfluidics is a cutting-edge technique that provides a new approach for producing nanoparticles (NPs) with controlled properties for a variety of applications. The current study's goal was to engineer repaglinide smart nanoparticles (Rp-Nc) utilizing microfluidic technology (Dolomite Y shape), and then to perform in-vitro, in-vivo, and toxicity evaluations of them. This method effectively generated nanocrystals with average particle sizes of 71.31 ± 11 nm and a polydispersity index (PDI) of 0.072 ± 12. The fabricated Rp's crystallinity was verified by Differential scanning calorimetry (DSC) and Powder X-ray diffraction (PXRD). In comparison to the raw and commercially available tablets, the fabricated Rp's nanoparticles resulted in a higher saturation solubility and dissolving rate (p < 0.05). Rp nanocrystals had a considerably lower (p < 0.05) IC50 value than that of the raw drug and commercial tablets. Moreover, Rp nanocrystals at the 0.5 and 1 mg/kg demonstrated a significant decrease in blood glucose level (mg/dL, p < 0.001, n = 8) compared to its counterparts. Rp nanocrystals at the 0.5 mg/kg demonstrated a significant decrease (p < 0.001, n = 8) in blood glucose compared to its counterparts at a dose of 1 mg/kg. The selected animal model's histological analyses and the effect of Rp nanocrystals on several internal organs were determined to be equivalent to those of the control animal group. The findings of the present study indicated that nanocrystals of Rp with improved anti-diabetic properties and safety profiles can be successfully produced using controlled microfluidic technology, an innovative drug delivery system (DDS) approach.

In Situ Observations Reveal the Five-fold Twin-Involved Growth of Gold Nanorods by Particle Attachment.

Crystallization plays a critical role in determining crystal size, purity and morphology. Therefore, uncovering the growth dynamics of nanoparticles (NPs) atomically is important for the controllable fabrication of nanocrystals with desired geometry and properties. Herein, we conducted in situ atomic-scale observations on the growth of Au nanorods (NRs) by particle attachment within an aberration-corrected transmission electron microscope (AC-TEM). The results show that the attachment of spherical colloidal Au NPs with a size of about 10 nm involves the formation and growth of neck-like (NL) structures, followed by five-fold twin intermediate states and total atomic rearrangement. The statistical analyses show that the length and diameter of Au NRs can be well regulated by the number of tip-to-tip Au NPs and the size of colloidal Au NPs, respectively. The results highlight five-fold twin-involved particle attachment in spherical Au NPs with a size of 3-14 nm, and provide insights into the fabrication of Au NRs using irradiation chemistry.

Synthesis, characterization, and evaluation of Hesperetin nanocrystals for regenerative dentistry

Hesperetin (HS), a metabolite of hesperidin, is a polyphenolic component of citrus fruits. This ingredient has a potential role in bone strength and the osteogenic differentiation. The bone loss in the orofacial region may occur due to the inflammation response of host tissues. Nanotechnology applications have been harshly entered the field of regenerative medicine to improve the efficacy of the materials and substances. In the current study, the hesperetin nanocrystals were synthesized and characterized. Then, the anti-inflammatory and antioxidative effects of these nanocrystals were evaluated on inflamed human Dental Pulp Stem Cells (hDPSCs) and monocytes (U937). Moreover, the osteoinduction capacity of these nanocrystals was assessed by gene and protein expression levels of osteogenic specific markers including RUNX2, ALP, OCN, Col1a1, and BSP in hDPSCs. The deposition of calcium nodules in the presence of hesperetin and hesperetin nanocrystals was also assessed. The results revealed the successful fabrication of hesperetin nanocrystals with an average size of 100 nm. The levels of TNF, IL6, and reactive oxygen species (ROS) in inflamed hDPSCs and U937 significantly decreased in the presence of hesperetin nanocrystals. Furthermore, these nanocrystals induced osteogenic differentiation in hDPSCs. These results demonstrated the positive and effective role of fabricated nanocrystal forms of this natural ingredient for regenerative medicine purposes.

Facile fabrication of MoS2 nanocrystals confined in waste leather derived N, P co-doped carbon fiber for long-lifespan of sodium/potassium ion batteries

Due to its slow kinetics and complicated multiphase development during cycling, developing anode materials for sodium/potassium-ion batteries (SIBs/PIBs) with high-rate and long-cycle simultaneously is still crucial and challenging. Additionally, the application of abundantly available, waste biomass to energy storage device has become a research hotspot. Herein, using waste leather as the adsorbent and bioreactor, we facilely fabricating the leather derived N/P co-doped carbon fiber composite with MoS2 nanocrystals after sulfuration treatment. Due to the intrinsic advantage of texture and component of collagen fiber, the ultrasmall MoS2 nanocrystals are evenly embedded with N/P co-doped carbon fibers. As expected, the MoS2/NP-C anode shows enhanced sodium/potassium storage capacity. It exhibits a high specific capacity (368 mAh g−1 at 0.2 A g−1) for PIBs and amazing long-term cycling qualities (241 mAh g−1 at 1 A g−1 even after 2500 cycles) for SIBs. This work provides further insight into the application of waste biomass for fabricating nanocomposite in energy storage.

Directing the Architecture of Surface-Clean Cu2O for CO Electroreduction.

Tailoring the morphology of nanocrystals is a promising way to enhance their catalytic performance. In most previous shape-controlled synthesis strategies, surfactants are inevitable due to their capability to stabilize different facets. However, the adsorbed surfactants block the intrinsic active sites of the nanocrystals, reducing their catalytic performance. For now, strategies to control the morphology without surfactants are still limited but necessary. Herein, a facile surfactant-free synthesis method is developed to regulate the morphology of Cu2O nanocrystals (e.g., solid nanocube, concave nanocube, cubic framework, branching nanocube, branching concave nanocube, and branching cubic framework) to enhance the electrocatalytic performance for the conversion of CO to n-propanol. Specifically, the Cu2O branching cubic framework (BCF-Cu2O), which is difficult to fabricate using previous surfactant-free methods, is fabricated by combining the concentration depletion effect and the oxidation etching process. More significantly, the BCF-Cu2O-derived catalyst (BCF) presents the highest n-propanol current density (-0.85 mA cm-2) at -0.45 V versus the reversible hydrogen electrode (VRHE), which is fivefold higher than that of the surfactant-coated Cu2O nanocube-derived catalyst (SFC, -0.17 mA cm-2). In terms of the n-propanol Faradaic efficiency in CO electroreduction, that of the BCF exhibits a 41% increase at -0.45 VRHE as compared with SFC. The high catalytic activity of the BCF that results from the clean surface and the coexistence of Cu(100) and Cu(110) in the lattice is well-supported by density functional theory calculations. Thus, this work presents an important paradigm for the facile fabrication of surface-clean nanocrystals with an enhanced application performance.

Defect Engineering of Ceria Nanocrystals for Enhanced Catalysis via a High-Entropy Oxide Strategy.

Introducing transition-metal components to ceria (CeO2) is important to tailor the surface redox properties for a broad scope of applications. The emergence of high-entropy oxides (HEOs) has brought transformative opportunities for oxygen defect engineering in ceria yet has been hindered by the difficulty in controllably introducing transition metals to the bulk lattice of ceria. Here, we report the fabrication of ceria-based nanocrystals with surface-confined atomic HEO layers for enhanced catalysis. The increased covalency of the transition-metal–oxygen bonds at the HEO–CeO2 interface promotes the formation of surface oxygen vacancies, enabling efficient oxygen activation and replenishment for enhanced CO oxidation capabilities. Understanding the structural heterogeneity involving bulk and surface oxygen defects in nanostructured HEOs provides useful insights into rational design of atomically precise metal oxides, whose increased compositional and structural complexities give rise to expanded functionalities.

Three‐Dimensional Porous Low‐Defect Carbon Nanotube and Graphene Network Supported Rh Nanocrystals as Efficient Methanol Oxidation Electrocatalysts

AbstractWith the rapid economic development and urgent environmental demands, the direct methanol fuel cell (DMFC) as one of environmental‐friendly energy‐conversion systems has attracted wide attention in the world, while the insufficient activity and low structural stability of the anode Pt/carbon catalyst largely deteriorate its overall performance. Herein, we report a facile and cost‐effective bottom‐up method to the fabrication of rhodium nanocrystals supported by three‐dimensional (3D) porous hybrid networks constructed from low‐defect carbon nanotubes and reduced graphene oxide (Rh/LCNT‐RGO) as Pt‐alternative electrocatalysts for DMFC. Such a structural design gives the resultant Rh/LCNT‐RGO hybrid a series of fantastic architectural advantages, such as the large specific surface area of 3D interconnected graphene configuration, high electrical conductivity of low‐defect carbon nanotubes, and abundant catalytically active sites of well‐dispersive Rh nanocrystals. As a consequence, the Rh/LCNT‐RGO hybrid displays unusual catalytic abilities towards the methanol electrooxidation, including a large electrochemically active surface area of 123.8 m2 g−1, a high mass activity of 1228.5 mA mg−1, strong poison tolerance, and long lifespan, far surpassing those of reference Rh/carbon black, Rh/acid‐treated CNT, and Rh/RGO catalysts.