Electrochemical partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni via coupled oxidation of an interfacing NiAl intermetallic compound for robust hydrogen evolution

Ni-based porous electrocatalysts have been widely used in the hydrogen evolution reaction(HER)in alkaline water electrolysis,and the catalysts are produced by selective leaching of Al from Ni-Al alloys.It is well known that chemical leaching of Ni-Al intermetallic compound(IMC)generates a high surface area in Ni(OH)_(2).However,the Ni(OH)_(2) produced by leaching the Ni-Al intermetallic compound retards the hydrogen evolution reaction,which is attributed to its weak hydrogen adsorption energy.In this study,we controlled the chemical state of Ni using plasma vapor deposition(PVD)followed by heat treatment,selective Al leaching,and electrochemical reduction.X-ray diffraction(XRD),scanning microscopy(SEM),transmission electron microscopy(TEM),and energy-dispersive X-ray spectroscopy(EDS)were used to confirm the phase evolution of the electrocatalysts during fabrication.We reveal that the heat-treated Ni-Al alloy with a thick Ni2Al3surface layer underwent selective Al leaching and produced biphasic interfaces comprising Ni(OH)_(2) and NiAl IMCs at the edges of the grains in the outermost surface layer.Coupled oxidation of the interfacing NiAl IMCs facilitated the partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni in the grains during electrochemical reduction,as confirmed by X-ray photoelectron spectroscopy(XPS).An electrocatalyst containing partially reduced Ni(OH)_(2)/Ni exhibited an overpotential of 54 mV at 10 mA/cm^(2) in a half-cell measurement,and a cell voltage of 1.675 V at 0.4 A/cm2for single-cell operation.A combined experimental and theoretical study(density functional theory calculations)revealed that the superior HER activity was attributed to the presence of partially reduced metallic Ni with various defects and residual Al,which facilitated water adsorption,dissociation,and finally hydrogen evolution.

Partial Dynamic Dimension Reduction for Conditional Mean in Regression

In many regression analysis,the authors are interested in regression mean of response variate given predictors,not its the conditional distribution.This paper is concerned with dimension reduction of predictors in sense of mean function of response conditioning on predictors.The authors introduce the notion of partial dynamic central mean dimension reduction subspace,different from central mean dimension reduction subspace,it has varying subspace in the domain of predictors,and its structural dimensionality may not be the same point by point.The authors study the property of partial dynamic central mean dimension reduction subspace,and develop estimated methods called dynamic ordinary least squares and dynamic principal Hessian directions,which are extension of ordinary least squares and principal Hessian directions based on central mean dimension reduction subspace.The kernel estimate methods for dynamic ordinary least squares and dynamic Principal Hessian Directions are employed,and large sample properties of estimators are given under the regular conditions.Simulations and real data analysis demonstrate that they are effective.

Tf_2O-TMDS combination for the direct reductive transformation of secondary amides to aldimines,aldehydes, and/or amines

The direct partial reduction of highly stable secondary amides to more reactive aldimines and aldehydes is a challenging yet highly demanding transformation. In this context, only three methods have been reported. We report herein an improved version of the Charette's method. Our protocol consists of activation of secondary amides with triflic anhydride/2-fluoropyridine,and partial reduction of the resulting intermediates with 1,1,3,3-tetramethyldisiloxane(TMDS), which delivered aldimines or aldehydes upon acidic hydrolysis. Aromatic amides were reduced to the corresponding aldimines in 85%–100% NMR yields,and yields(NMR) from aliphatic amides were 72%–86%. Acidic hydrolysis of the aldimine intermediates afforded, in one-pot,the corresponding aldehydes in 80%–96% yields. A simple protocol was established to isolate labile aldimines in pure form in92%–96% yields. The improved method gave generally higher yields as compared to the known ones, and features the use of cheaper and more atom-economical TMDS as a chemoselective reducing agent. In addition, a convenient extraction protocol has been established to allow the isolation of amines, which constitutes a mild method for the N-deacylation of amides, another highly desirable transformation. The extended method retains the advantages of the original method of Charette in terms of mild conditions, good functional group tolerance, and excellent chemoselectivity.

New method for high performance multiply-accumulator design

This study presents a new method of 4-pipelined high-performance split multiply-accumulator (MAC) architecture, which is capable of supporting multiple precisions developed for media processors. To speed up the design further, a novel partial product compression circuit based on interleaved adders and a modified hybrid partial product reduction tree (PPRT) scheme are proposed. The MAC can perform 1-way 32-bit, 4-way 16-bit signed/unsigned multiply or multiply-accumulate operations and 2-way parallel multiply add (PMADD) operations at a high frequency of 1.25 GHz under worst-case conditions and 1.67 GHz under typical-case conditions, respectively. Compared with the MAC in 32-bit microprocessor without interlocked piped stages (MIPS), the proposed design shows a great advantage in speed. Moreover, an improvement of up to 32% in throughput is achieved. The MAC design has been fabricated with Taiwan Semiconductor Manufacturing Company (TSMC) 90-nm CMOS standard cell technology and has passed a functional test.