高熵纳米合金在电化学催化中的应用

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO₂ reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.     

Quantum interference in carbon nanotube intramolecular junction

The quantum conductance oscillations (QCOs) of the intramolecular junction (IMJ) composed of two single-wall carbon nanotubes (SWNTs) have been studied by using a π-orbital only tight-binding (TB) model and a Green’s function technique. It is found that in the IMJs in addition to the rapid QCO frequencies corresponding to the constituent tubes there exist also their sum frequencies. The slow QCO frequencies of the IMJ will be different from those of its corresponding two perfect tubes if they have different chiral angles.     

Quantum interference in nanotube electron waveguides

We have calculated the quantum conductance of single-walled carbon nanotube (SWNT) waveguide by using a tight binding-based Greens function approach. Our calculations show that the slow conductance oscillations as well as the fast conductance oscillations are manifestations of the intrinsic quantum interference properties of the conducting SWNTs, being independent of the defect and disorder of the SWNTs. And zigzag type tubes do not show the slow oscillations. The SWNT electron waveguide is also found to have distinctly different transport behavior depending on whether or not the length of the tube is commensurate with a (3N+1) rule, with N the number of basic carbon repeat units along the nanotube length.     

Preparation of monolithic silica column with strong cation-exchange stationary phase for capillary electrochromatography

A monolithic silica based strong cation-exchange stationary phase was successfully prepared for capillary electrochromatography. The monolithic silica matrix from a sol-gel process was chemically modified by treatment with 3-mercaptopropyltrimethoxysilane followed by a chemical oxidation procedure to produce the desired function. The strong cation-exchange stationary phase was characterized by its substantial and stable electroosmotic flow (EOF), and it was observed that the EOF value of the prepared column remained almost unchanged at different buffer pH values and slowly decreased with increasing phosphate concentration in the mobile phase. The monolithic silica column with strong cation-exchange stationary phase has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). The column efficiencies for the tested beta-blockers varied from 210,000 to 340,000 plates/m. A peak compression effect was observed for atenolol with the mobile phase having a low phosphate concentration.     

Complete condensation in a zero range process on scale-free networks

We study a zero range process on scale-free networks in order to investigate how network structure influences particle dynamics. The zero range process is defined with the rate p(n) = n(delta) at which particles hop out of nodes with n particles. We show analytically that a complete condensation occurs when delta < or = delta(c) triple bond 1/(gamma-1) where gamma is the degree distribution exponent of the underlying networks. In the complete condensation, those nodes whose degree is higher than a threshold are occupied by macroscopic numbers of particles, while the other nodes are occupied by negligible numbers of particles. We also show numerically that the relaxation time follows a power-law scaling tau approximately L(z) with the network size L and a dynamic exponent z in the condensed phase.     

Body-centered-cubic Ni and its magnetic properties

The body-centered-cubic (bcc) phase of Ni, which does not exist in nature, has been achieved as a thin film on GaAs(001) at 170 K via molecular beam epitaxy. The bcc Ni is ferromagnetic with a Curie temperature of 456 K and possesses a magnetic moment of 0.52+/-0.08 micro(B)/atom. The cubic magnetocrystalline anisotropy of bcc Ni is determined to be +4.0x10(5) ergs x cm(-3), as opposed to -5.7x10(4) ergs x cm(-3) for the naturally occurring face-centered-cubic (fcc) Ni. This sharp contrast in the magnetic anisotropy is attributed to the different electronic band structures between bcc Ni and fcc Ni, which are determined using angle-resolved photoemission with synchrotron radiation.     

Asymmetrically coupled directed percolation systems

We introduce a dynamical model of coupled directed percolation systems with two particle species. The two species A and B are coupled asymmetrically in that A particles branch B particles, whereas B particles prey on A particles. This model may describe epidemic spreading controlled by reactive immunization agents. We study nonequilibrium phase transitions with attention focused on the multicritical point where both species undergo the absorbing phase transition simultaneously. In one dimension, we find that the inhibitory coupling from B to A is irrelevant and the model belongs to the unidirectionally coupled directed percolation class. On the contrary, a mean-field analysis predicts that the inhibitory coupling is relevant and a new universality appears with a variable dynamic exponent. Numerical simulations on small-world networks confirm our predictions.     

Real-time evolution of the distribution of nanoparticles in an ultrathin-polymer-film-based waveguide

We report a novel application of an ultrathin-polymer-film-based, resonance-enhanced x-ray waveguide as a real-time nanoprobe for elucidating dilute, yet disordered, gold nanoparticles embedded in the polymer matrix. This nanoprobe promises a sensitivity enhancement of several orders of magnitude, hence revealing in real time the lateral nanoparticle distribution with subnanometer spatial resolution. We observed that the motion of the nanoparticles is strongly anisotropic, with in-plane coalescence taking place more rapidly than out-of-plane diffusion, which can ultimately facilitate the formation of two-dimensional structures.     

Search for D0-D0 mixing in D0 --> K+ pi(-) decays and measurement of the doubly-Cabibbo-suppressed decay rate

We have searched for mixing in the D(0)-D (0) system by measuring the decay-time distribution of D(0) --> K(+) pi(-) decays. The analysis uses 90 fb(-1) of data collected by the Belle detector at the KEKB e(+) e(-) collider. We fit the decay-time distribution for the mixing parameters x' and y' and also for the parameter R(D), which is the ratio of the rate for the doubly-Cabibbo-suppressed decay D(0)--> K+ pi(-) to that for the Cabibbo-favored decay D(0)--> K-pi(+). We do these fits both assuming CP conservation and allowing for CP violation. We use a frequentist method to obtain a 95% C.L. region in the x'(2) - y' plane. Assuming no mixing, we measure R(D) = (0.381 +/- 0.017(+0.008)(-0.016))%.     

Determination of /Vub/ from measurements of the inclusive charmless semileptonic partial rates of B mesons using full reconstruction tags

We present a measurement of the Cabibbo-Kobayashi-Maskawa matrix element /Vub/, based on 253 fb(-1) of data collected by the Belle detector at the KEKB e+ e- asymmetric collider. Events are tagged by fully reconstructing one of the B mesons, produced in pairs from Gamma(4S). The signal for b --> u semileptonic decay is distinguished from the b --> c background using the hadronic mass Mx, the leptonic invariant mass squared q2 and the variable P+ [triple bond] Ex - /px/. The results are obtained for events with p(l)* > or = 1 GeV/c, in three kinematic regions (1) Mx < 1.7 GeV/c2, (2) Mx < 1.7 GeV/c2 combined with q2 > 8 GeV2/c2, and by (3) P+ < 0.66 GeV/c. The matrix element /Vub/ is found to be (4.09 +/- 0.19 +/- 0.20(+0.14) -0.15 +/- 0.18) x 10(-3), where the errors are statistical, systematic including Monte Carlo modeling, theoretical, and from shape function parameter determination, respectively.