The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic ...centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect‐rich Bi nanoplates as an efficient noble‐metal‐free N2 reduction electrocatalyst via a low‐temperature plasma bombardment approach. When exclusively using 1H NMR measurements with N2 gas as a quantitative testing method, the defect‐rich Bi(110) nanoplates achieved a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solution at ambient conditions.
Beneficial defects: Defect‐rich bismuth nanoplates achieve a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solutions at ambient conditions because of their poor binding with H adatoms, which increases the selectivity and production rate. Also, 1H NMR measurements with N2 gas ware used as a quantitative test method in aqueous electrolytes.
Although single-atomically dispersed metal-N
on carbon support (M-NC) has great potential in heterogeneous catalysis, the scalable synthesis of such single-atom catalysts (SACs) with high-loading ...metal-N
is greatly challenging since the loading and single-atomic dispersion have to be balanced at high temperature for forming metal-N
. Herein, we develop a general cascade anchoring strategy for the mass production of a series of M-NC SACs with a metal loading up to 12.1 wt%. Systematic investigation reveals that the chelation of metal ions, physical isolation of chelate complex upon high loading, and the binding with N-species at elevated temperature are essential to achieving high-loading M-NC SACs. As a demonstration, high-loading Fe-NC SAC shows superior electrocatalytic performance for O
reduction and Ni-NC SAC exhibits high electrocatalytic activity for CO
reduction. The strategy paves a universal way to produce stable M-NC SAC with high-density metal-N
sites for diverse high-performance applications.
Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum‐free electrocatalysts for large‐scale electrochemical production of pure hydrogen fuel, ...but most state‐of‐the‐art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high‐entropy CuNiMoFe surface is reported to hold great promise as cost‐effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high‐entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm−2 in 1 m KOH and pH 7 buffer electrolytes, respectively; ≈46‐ and ≈14‐fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high‐performance nonacidic HER electrocatalytic electrodes in water electrolysis.
Nonprecious nanoporous multielemental alloy electrodes composed of electroactive surface high‐entropy CuNiMoFe alloy hold great promise as cost‐effective electrocatalysts for hydrogen evolution reaction (HER) in nonacidic media. Associated with hierarchical nanoporous architecture to facilitate electron transfer and offer abundant high‐entropy CuNiMoFe active sites, the nanoporous CuAlNiMoFe hybrid electrode exhibits remarkably enhanced HER activity and durability.
Hardware implementation of artificial synaptic devices that emulate the functions of biological synapses is inspired by the biological neuromorphic system and has drawn considerable interest. Here, a ...three‐terminal ferrite synaptic device based on a topotactic phase transition between crystalline phases is presented. The electrolyte‐gating‐controlled topotactic phase transformation between brownmillerite SrFeO2.5 and perovskite SrFeO3−δ is confirmed from the examination of the crystal and electronic structure. A synaptic transistor with electrolyte‐gated ferrite films by harnessing gate‐controllable multilevel conduction states, which originate from many distinct oxygen‐deficient perovskite structures of SrFeOx induced by topotactic phase transformation, is successfully constructed. This three‐terminal artificial synapse can mimic important synaptic functions, such as synaptic plasticity and spike‐timing‐dependent plasticity. Simulations of a neural network consisting of ferrite synaptic transistors indicate that the system offers high classification accuracy. These results provide insight into the potential application of advanced topotactic phase transformation materials for designing artificial synapses with high performance.
A ferrite synaptic transistor with topotactic transformation is presented. The electrolyte‐gating‐controlled topotactic phase transformation between the brownmillerite SrFeO2.5 and perovskite SrFeO3−δ is confirmed by the crystal and electronic structure measurements. This ferrite synaptic transistor can mimic important synaptic functions such as synaptic plasticity and spike‐timing‐dependent plasticity.
Major depressive disorder (MDD) is common and disabling, but its neuropathophysiology remains unclear. Most studies of functional brain networks in MDD have had limited statistical power and data ...analysis approaches have varied widely. The REST-meta-MDD Project of resting-state fMRI (R-fMRI) addresses these issues. Twenty-five research groups in China established the REST-meta-MDD Consortium by contributing R-fMRI data from 1,300 patients with MDD and 1,128 normal controls (NCs). Data were preprocessed locally with a standardized protocol before aggregated group analyses. We focused on functional connectivity (FC) within the default mode network (DMN), frequently reported to be increased in MDD. Instead, we found decreased DMN FC when we compared 848 patients with MDD to 794 NCs from 17 sites after data exclusion. We found FC reduction only in recurrent MDD, not in first-episode drug-naïve MDD. Decreased DMN FC was associated with medication usage but not with MDD duration. DMN FC was also positively related to symptom severity but only in recurrent MDD. Exploratory analyses also revealed alterations in FC of visual, sensory-motor, and dorsal attention networks in MDD. We confirmed the key role of DMN in MDD but found reduced rather than increased FC within the DMN. Future studies should test whether decreased DMN FC mediates response to treatment. All R-fMRI indices of data contributed by the REST-meta-MDD consortium are being shared publicly via the R-fMRI Maps Project.
The exploration of new efficient OER electrocatalysts based on nonprecious metals and the understanding of the relationship between activity and structure of electrocatalysts are important to advance ...electrochemical water oxidation. Herein, we developed an efficient OER electrocatalyst with nickel boride (Ni3B) nanoparticles as cores and nickel(II) borate (Ni‐Bi) as shells (Ni‐Bi@NB) via a very simple and facile aqueous reaction. This electrocatalyst exhibited a small overpotential of 302 mV at 10 mA cm−2 and Tafel slope of 52 mV dec−1. More interestingly, it was found that the OER activity of Ni‐Bi@NB was closely dependent on the crystallinity of the Ni‐Bi shells. The partially crystalline Ni‐Bi catalyst exhibited much higher activity than the amorphous or crystalline analogues; this higher activity originated from the enhanced intrinsic activity of the catalytic sites. These findings open up opportunities to explore nickel(II) borates as a new class of efficient nonprecious metal OER electrocatalysts, and to improve the electrocatalyst performance by modulating their crystallinity.
A new winner! Crystallinity‐dependent activity was demonstrated on a new efficient electrocatalyst for the oxygen evolution reaction (OER) which consists of a nickel(II) borate thin layer on nickel boride (NB) nanoparticles (Ni‐Bi@NB) (see figure). The partially crystalline Ni‐Bi catalyst exhibits excellent OER performance.
Molecular rotors have played an important role in recent materials chemistry. Although several studies on functional materials containing molecular rotors have been reported for fluorescence sensing, ...this concept has yet to be realized in two-dimensional (2D) materials. Here we report the preparation of all-carbon, π-conjugated 2D porous organic nanosheets, named NUS-24, which contain flexible tetraphenylethylene (TPE) units as the molecular rotors. NUS-24 nanosheets exhibit high stability, large lateral size, and ultrathin thickness (2-5 nm). The dynamic TPE rotors exposed on the surface of NUS-24 nanosheets can be restricted in the aggregated state with different water fractions, which is reminiscent of the aggregation-induced emission mechanism, thereby leading to the size-selective turn-on fluorescence by volatile organic compounds. Significantly, the ultrathin 2D nanosheets and its composite membranes show much higher sensitivity and selectivity toward Fe
ions and nitro-containing compounds sensing, suggesting their potential applications in explosive detection and environmental monitoring.
Solar‐driven high‐efficiency and direct conversion of methane into high‐value‐added liquid oxygenates against overoxidation remains a great challenge. Herein, facile and mass fabrication of low‐cost ...tungsten single‐atom photocatalysts is achieved by directly calcining urea and sodium tungstate under atmosphere (W‐SA‐PCN‐m, urea amount m = 7.5, 15, 30, and 150 g). The single‐atom photocatalysts can manage H2O2 in situ generation and decomposition into ·OH, thus achieving highly efficient CH4 photooxidation in water vapor under mild conditions. Systematic investigations demonstrate that integration of multifunctions of methane activation, H2O2 generation, and decomposition into one photocatalyst can dramatically promote methane conversion to C1 oxygenates with a yield as high as 4956 µmol gcat−1, superior to that of the most reported non‐precious photocatalysts. Liquid–solid phase transition can induce the products to facilely switch in from HCOOH to CH3OH by pulling the catalyst above water with CH3OH/HCOOH ratio from 10% (in H2O) to 80% (above H2O).
The mass fabrication of low‐cost tungsten single atom photocatalysts is achieved by directly calcining urea and sodium tungstate under atmosphere. These single‐atom photocatalysts can manage H2O2 in situ generation and decomposition into ·OH to achieve highly efficient CH4 photooxidation in water vapor, and the products can be facilely switched from HCOOH to CH3OH by the liquid–solid phase transition.
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