High-entropy oxides (HEOs) exhibit great prospects owing to their varied composition, chemical adaptability, adjustable light-absorption ability, and strong stability. In this study, we report a strategy to synthesize a series of porous high-entropy spinel oxide (HESO) nanofibers (NFs) at a low temperature of 400 °C by a sol-gel electrospinning technique. The key lies in selecting six acetylacetonate salt precursors with similar coordination abilities, maintaining a high-entropy disordered state during the transformation from stable sols to gel NFs. The as-synthesized HESO NFs of (NiCuMnCoZnFe)3O4 show a high specific surface area of 66.48 m2/g, a diverse elemental composition, a dual bandgap, half-metallicity property, and abundant defects. The diverse elements provide various synergistic catalytic sites, and oxygen vacancies act as active sites for electron-hole separation, while the half-metallicity and dual-bandgap structure offer excellent light absorption ability, thus expanding its applicability to a wide range of photocatalytic processes. As a result, the HESO NFs can efficiently convert CO2 into CH4 and CO with high yields of 8.03 and 15.89 μmol g-1 h-1, respectively, without using photosensitizers or sacrificial agents.
2D layered Bi2WO6 (BWO) is a widely used attractive photocatalyst for degrading VOCs, but the low visible-light utilization and the easy stacking 2D nanosheets (NSs) limit photocatalysis efficiency and stability. Here, inspired by Eucalyptus, a synergistic strategy of multiscale domain-confinement and electrostatic force action, based on electrospinning is proposed, for fabricating a heteromorphic BWO photocatalyst. It is found that BWO NSs can grow radially in an orderly spaced arrangement along BWO nanofibers (NFs) during sintering, thereby forming 1D/2D BWO junctions like eucalyptus leaves. This interpenetrating 1D/2D network structure not only solves the easy stacking problem of BWO NSs but also selectively exposes the {010} crystal planes that exhibit efficient hole oxidation. In addition, this peculiar structure enriches electrons at the 1D/2D interface to avoid carrier recombination, thus improving the photocatalytic activity. The photocatalyst material with a reduced bandgap width from 2.56 to 2.49 eV can rapidly degrade 100% of acetaldehyde under visible light without using sacrificial agents and photosensitizers and shows superior stability for eight cycles without any decay. This study provides a feasible method to synthesize an efficient and stable BWO photocatalyst.
Magnetic field regulation is an effective strategy to improve the photocatalytic activity of magnetic semiconductor photocatalysts, but it is not suitable for widely used nonmagnetic photocatalytic semiconductors. Here, we report a Zeeman effect-driven spin-polarized band splitting phenomenon in diluted magnetic semiconductors that show efficient photocatalytic CO2 reduction under visible-light irradiation. A flexible Ni2+-doped BaTiO3 nanofiber film is used as the diluted magnetic semiconductor model to prove this concept. The interstitial Ni2+ dopant induces the spin-polarized bands in Ni-BaTiO3 nanofibers to split under light excitation, generating spin-excited electrons and holes. This Zeeman effect induced by the magnetic field is more obvious since it intensifies the spin-polarized band splitting and generates more spin-excited electrons and holes, suppressing the carrier recombination and extending the carrier lifetime for CO(2 )photoreduction. As a result, the evolution rates of CO and CH4 are as high as 86.47 and 96.06 mu mol/g/h under a small magnetic field of 50 mT. The proposed mechanism of Zeeman effect-driven spin-polarized band splitting is feasible to improve the CO(2 )photoreduction efficiency of broadly applied diluted magnetic semiconductors.
Cobalt (Co) is an efficient oxygen reduction reaction (ORR) catalyst but suffers from issues of easy deactivation and instability. Here, it shows that ZrO2 can stabilize Co through interface electron coupling and enables highly efficient 4e- ORR catalysis. Porous carbon nanofibers loaded with dispersed Co-nanodots (≈10 nm, 9.63 wt%) and ZrO2 nanoparticles are synthesized as the catalyst. The electron transfer from the metallic Co to ZrO2 causes interface-oriented electron enrichment that promotes the activation and conversion of O2, improving the efficiency of 4e- transfer. Moreover, the simulation results show that ZrO2 acts like an electron reservoir to store electrons from Co and slowly release them to the interface, solving the easy deactivation problem of Co. The catalyst exhibits a high half-wave potential (E1/2) of 0.84 V, which only decreases by 3.6 mV after 10 000 cycles, showing great stability. Particularly, the enhanced spin polarization of Co in a magnetic field reinforces the interface electron coupling that increases the E1/2 to 0.864 V and decreases the energy barrier of ORR from 0.81 to 0.63 eV, confirming that the proposed strategy is effective for constructing efficient and stable ORR catalysts.
Dealing with bone defects is a significant challenge to global health. Electrospinning in bone tissue engineering has emerged as a solution to this problem. In this study, we designed a PVDF-b-PTFE block copolymer by incorporating TFE, which induced a phase shift in PVDF fromαtoβ, thereby enhancing the piezoelectric effect. Utilizing the electrospinning process, we not only converted the material into a film with a significant surface area and high porosity but also intensified the piezoelectric effect. Then we used polydopamine to immobilize BMP-2 onto PVDF-b-PTFE electrospun nanofibrous membranes, achieving a controlled release of BMP-2. The scaffold's characters were examined using SEM and XRD. To assess its osteogenic effectsin vitro, we monitored the proliferation of MC3T3-E1 cells on the fibers, conducted ARS staining, and measured the expression of osteogenic genes.In vivo, bone regeneration effects were analyzed through micro-CT scanning and HE staining. ELISA assays confirmed that the sustained release of BMP-2 can be maintained for at least 28 d. SEM images and CCK-8 results demonstrated enhanced cell viability and improved adhesion in the experimental group. Furthermore, the experimental group exhibited more calcium nodules and higher expression levels of osteogenic genes, including COL-I, OCN, and RUNX2. HE staining and micro-CT scans revealed enhanced bone tissue regeneration in the defective area of the PDB group. Through extensive experimentation, we evaluated the scaffold's effectiveness in augmenting osteoblast proliferation and differentiation. This study emphasized the potential of piezoelectric PVDF-b-PTFE nanofibrous membranes with controlled BMP-2 release as a promising approach for bone tissue engineering, providing a viable solution for addressing bone defects.
The emerging transition metal-nitrogen-carbon (MNC) materials are considered as a promising oxygen reduction reaction (ORR) catalyst system to substitute expensive Pt/C catalysts due to their high surface area and potential high catalytic activity. However, MNC catalysts are easy to be attacked by the ORR byproducts that easily lead to the deactivation of metal active sites. Moreover, a high metal loading affects the mass transfer and stability, but a low loading delivers inferior catalytic activity. Here, a new strategy of designing ZrO2 quantum dots and N-complex as dual chemical ligands in N-doped bubble-like porous carbon nanofibers (N-BPCNFs) to stabilize copper (Cu) by forming CuZrO3-x /ZrO2 heterostructures and CuN ligands with a high loading of 40.5 wt.% is reported. While the highly porous architecture design of N-BPCNFs builds a large solidelectrolytegas phase interface and promotes mass transfer. The preliminary results show that the half-wave potential of the catalyst reaches 0.856 V, and only decreases 0.026 V after 10 000 cycles, exhibiting excellent stability. The proposed strategy of stabilizing metal active sites with both heterostructures and CuN ligands is feasible and scalable for developing high metal loading ORR catalyst.
Oxide ceramic microfibers with low thermal conductivity, high temperature, and corrosion resistance have been widely used in the field of thermal insulation. When the fiber diameter is reduced to the nanoscale (<1000 nm), the high specific surface area and porosity brought by the diameter refinement endow these nanofibers with unique thermal, optical, electrical and other properties, which are expected to be applied in advanced high-tech fields. Oxide ceramic micro-nanofibers (MNFs) belong to a new structural ceramic system, but they suffer from intrinsic hardness and brittleness. We have been committed to developing new textile technologies and fabricating flexible oxide ceramic MNFs. In this review, the development status of oxide ceramic MNFs and their applications are first briefly summarized. Then, the definition of flexibility and flexibility mechanisms of MNFs, as well as the strategies and methods for fabricating flexible oxide ceramic MNFs are comprehensively discussed. Finally, our perspective on the future development of oxide ceramic MNFs is proposed. We suppose that they will develop toward the direction of flexibility, porosity, multifunctionality, thin film, and aerogels, and their functional applications will permeate from the traditional heat insulation to the emerging fields such as flexible electronics and batteries, intelligent artificial muscle, and industrial catalysis.
Achieving high selectivity and conversion efficiency simultaneously is a challenge for visible‐light‐driven photocatalytic CO2 reduction into CH4. Here, a facile nanofiber synthesis method and a new defect control strategy at room‐temperature are reported for the fabrication of flexible mesoporous black Nb2O5 nanofiber catalysts that contain abundant oxygen‐vacancies and unsaturated Nb dual‐sites, which are efficient towards photocatalytic production of CH4. The oxygen‐vacancy decreases the bandgap width of Nb2O5 from 3.01–2.25 eV, which broadens the light‐absorption range from ultraviolet to visible‐light, and the dual sites in the mesopores can easily adsorb CO2, so that the intermediate product of CO* can be spontaneously changed into *CHO. The formation of a highly stable NbCHO* intermediate at the dual sites is proposed to be the key feature determining selectivity. The preliminary results show that without using sacrificial agents and photosensitizers, the nanofiber catalyst achieves 64.8% selectivity for CH4 production with a high evolution rate of 19.5 µmol g−1 h−1 under visible‐light. Furthermore, the flexible catalyst film can be directly used in devices, showing appealing and broadly commercial applications.