构筑非晶/晶体NiFe-MOF@NiS异质结构催化剂增强大电流密度下水/海水氧化

电化学水分解作为一种生产高纯度氢气的绿色技术,虽然前景广阔,但阳极析氧反应(OER)动力学缓慢,严重制约了其能量转换效率.目前,电化学水分解系统主要以淡水作为原料.然而,大规模使用淡水进行分解无疑会给淡水资源带来沉重负担.相比之下,占水资源总量96%以上的海水,因其丰富的储量,成为替代淡水的理想选择.然而,由于海水中含有大量的氯离子,会引发与OER的竞争性氯析出反应(ClER)形成次氯酸盐(ClO^(–)),导致活性位点失活,严重降低催化剂的活性和稳定性.因此,如何在利用海水进行电化学水分解的同时,有效抑制ClER的发生,是当前亟待解决的科学问题.在最新催化剂研究中,金属有机框架(MOF)凭借其高孔隙率、大比表面积和分散的活性位点,在电化学水分解中展现出良好的性能.然而,MOF的电子导电性和OER反应能垒受限于氧原子p轨道与金属原子d轨道间的电子云重叠.因此,设计MOF活性位点的电子结构,促进自发电子转移,对于提升导电性和OER效率至关重要.界面工程能优化MOF活性位点的电子结构,增强局部电荷再分配,从而提高OER活性.为满足工业高电流密度需求,构建富含缺陷的异质结构是关键,其能暴露更多OER活性位点,优化质量传递,缩短电子迁移路径.结合高导电、可调电子结构的NiS晶体相,构建MOF非晶/NiS晶体异质界面,可调控电子结构并加速电荷转移.目前,关于MOF基非晶/晶异质界面催化剂用于海水氧化的报道尚少,这一方向具有巨大潜力.本文通过两步法耦合策略,成功在泡沫镍基底上制备了NiFe-MOF@NiS异质结构催化剂.首先,利用硫温和改性腐蚀方法在泡沫镍基体生长晶相NiS纳米片;随后,通过电沉积处理在NiS表面生长非晶相NiFe-MOF纳米颗粒.理论计算结果表明,NiFe-MOF和NiS之间的电子相互作用可以加速电荷转移,有效调节金属位点的d带中心,从而优化含氧中间体的吸附能力.与NiFe-MOF和NiS相比,NiFe-MOF@NiS/NF催化剂对OOH*中间体的吸附能力更为突出,这大大降低了速率决定步骤(O*→OOH*)的反应能垒,为高效催化OER提供了理论支撑.实验结果表明,在1 mol L^(‒1)KOH和碱性海水电解液中,NiFe-MOF@NiS/NF催化剂仅需要346和355 mV的低过电位,即可驱动500 mA cm^(–2)的大电流密度.Tafel斜率和电化学阻抗谱的结果表明,该催化剂具有较好的OER动力学特征.此外,质量活性和转换频率结果表明,NiFe-MOF@NiS/NF催化剂展现出良好的本征催化活性.多步恒电流阶梯曲线以及在100和500 mA cm‒2电流密度下的计时电位曲线结果表明,NiFe-MOF@NiS/NF催化剂具有出色的长期稳定性.通过对在碱性海水电解液OER反应后的NiFe-MOF@NiS/NF催化剂进行表征发现,在OER过程中,NiS物种会在阳极电压下自重构形成硫酸盐膜,可以显著抑制Cl–离子在催化剂表面的吸附,使NiFe-MOF@NiS/NF催化剂在海水电解质中具有强大的耐腐蚀性.这一特性使得NiFe-MOF@NiS/NF催化剂在碱性KOH和碱性海水中均能保持较好的OER活性和稳定性,性能超过了商业RuO_(2)以及大多数报道的其他MOF基的催化剂.综上所述,本文通过简便易行的合成策略,制备了高性能的NiFe-MOF@NiS异质结催化剂,其表现出高效电解海水性能和稳定性.本工作为合理设计高活性、稳定性、选择性的MOF基抗氯腐蚀催化剂以提高碱性海水的OER性能提供了新视角.

2D CoOOH Sheet-Encapsulated Ni2P into Tubular Arrays Realizing 1000 mA cm^-2-Level-Current-Density Hydrogen Evolution Over 100 h in Neutral Water

Water electrolysis at high current density(1000 mA cm-2 level)with excellent durability especially in neutral electrolyte is the pivotal issue for green hydrogen from experiment to industrialization.In addition to the high intrinsic activity determined by the electronic structure,electrocatalysts are also required to be capable of fast mass transfer(electrolyte recharge and bubble overflow)and high mechanical stability.Herein,the 2D CoOOH sheet-encapsulated Ni2P into tubular arrays electrocatalytic system was proposed and realized 1000 mA cm-2-levelcurrent-density hydrogen evolution over 100 h in neutral water.In designed catalysts,2D stack structure as an adaptive material can buffer the shock of electrolyte convection,hydrogen bubble rupture,and evolution through the release of stress,which insure the long cycle stability.Meanwhile,the rich porosity between stacked units contributed the good infiltration of electrolyte and slippage of hydrogen bubbles,guaranteeing electrolyte fast recharge and bubble evolution at the high-current catalysis.Beyond that,the electron structure modulation induced by interfacial charge transfer is also beneficial to enhance the intrinsic activity.Profoundly,the multiscale coordinated regulation will provide a guide to design high-efficiency industrial electrocatalysts.

Interface engineering of NiSe_(2) nanowrinkles/Ni_(5)P_(4)nanorods for boosting urea oxidation reaction at large current densities

Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption.In response,we report the coupled NiSe_(2)nanowrinkles with Ni_(5)P_(4)nanorods heterogeneous structure onto Ni foam(denoted as NiSe_(2)@Ni_(5)P_(4)/NF)through successive phosphorization and selenization strategy,in which the produced closely contacted interface could provide high-flux electron transfer pathways.Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni_(5)P_(4)to NiSe_(2),which is conducive to optimizing adsorption energy of urea molecules.As expected,the well-designed NiSe_(2)@Ni_(5)P_(4)/NF only requires the low potential of 1.402 V at the current density of 500 mA·cm^(-2).More importantly,a small Tafel slope of 27.6 mV·dec^(-1),a high turnover frequency(TOF)value of 1.037 s^(-1)as well as the prolonged stability of 950 h at the current density of 100 mA·cm^(-2)are also achieved.This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.

Controllable Ni/NiO interface engineering on N-doped carbon spheres for boosted alkaline water-to-hydrogen conversion by urea electrolysis

Interface engineering has gradually attracted substantial research interest in constructing active bifunctional catalysts toward urea electrolysis.The fundamental understanding of the crystallinity transition of the components on both sides of the interface is extremely significant for realizing controllable construction of catalysts through interface engineering,but it still remains a challenge.Herein,the Ni/NiO heterogenous nanoparticles are successfully fabricated on the porous N-doped carbon spheres by a facile hydrothermal and subsequent pyrolysis strategy.And for the first time we show the experimental observation that the Ni/NiO interface can be fine-tuned via simply tailoring the heating rate during pyrolysis process,in which the crystalline/amorphous or crystalline/crystalline Ni/NiO heterostructure is deliberately constructed on the porous N-doped carbon spheres(named as CA-Ni/NiO@NCS or CC-Ni/NiO@NCS,respectively).By taking advantage of the unique porous architecture and the synergistic effect between crystalline Ni and amorphous NiO,the well-designed CA-Ni/NiO@NCS displays more remarkable urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)activity than its crystalline/crystalline counterpart of CC-Ni/NiO@NCS.Particularly,the whole assembled two-electrode electrolytic cell using the elaborate CANi/NiO@NCS both as the anode and cathode can realize the current density of 10 mA·cm^(−2)at a super low voltage of 1.475 V(264 mV less than that of pure water electrolysis),as well as remarkable prolonged stability over 63 h.Besides,the H_(2)evolution driven by an AA battery and a commercial solar cell is also studied to enlighten practical applications for the future.

Nanovilli electrode boosts hydrogen evolution:A surface with superaerophobicity and superhydrophilicity

Although tremendous efforts have been paid on electrocatalysts toward efficient electrochemical hydrogen generation,breakthrough is still highly needed in the design and synthesis of wonderful non-precious-metal electrocatalyst.Herein,a nanovilli Ni2P electrode,which with superaerophobic and superhydropholic can significantly facilitate the mass and electron transfer was constructed via a facial morphology control strategy.Meanwhile,the substitution of sluggish oxygen evolution with urea oxidation,lowering the two-electrode cell voltage to only 1.48 volts to achieve a current density of 10 mA·cm^(-2).Thus,the as-constructed electrode achieves the operation of hydrogen generation by an AA battery.This work sheds new light on the exploration of other high-efficient electrocatalysts for hydrogen generation by using intermittent clean energy.

Semiparametric quantile-difference estimation for length-biased and right-censored data

Prevalent cohort studies frequently involve length-biased and right-censored data, a fact that has drawn considerable attention in survival analysis. In this article, we consider survival data arising from lengthbiased sampling, and propose a new semiparametric-model-based approach to estimate quantile differences of failure time. We establish the asymptotic properties of our new estimators theoretically under mild technical conditions, and propose a resampling method for estimating their asymptotic variance. We then conduct simulations to evaluate the empirical performance and efficiency of the proposed estimators, and demonstrate their application by a real data analysis.