Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

磷掺杂碳负载Zn_(x)P_(y)O_(z)常温常压下高效电催化合成氨

合成氨(NH_(3))的发展是现代工业进程和人类生存的基石。受氮气(N_(2))化学惰性的限制,当前的合成氨工业能源消耗高并且排放大量的二氧化碳。电化学氮气还原反应(NRR),是有望取代高能耗的Haber-Bosch(HB)合成法的一种绿色可持续的合成氨工艺。然而,因氮气以及析氢竞争富反应(HER)导致电催化氮气还原极低的NH_(3)产率和能量转换效率一直是目前人工固氮领域面临的挑战。在本文中,我们报道了一种具有丰富孔结构的磷掺杂碳(PC)负载Zn_(3)(PO_(4))_(2)/Zn_(2)P_(2)O_(7)纳米复合材料(h-PC/Zn_(3)(PO_(4))_(2)/Zn_(2)P_(2)O_(7)),在酸性和中性介质中将N_(2)高效催化转化为NH_(3)。其独特的分级多孔结构提高了表面粗糙度并加快了氮气在催化剂体相中的扩散,这有利于延长氮气在催化剂表面的停留时间以及提高活性位点的利用效率。而多组分的均匀分布可以调节电子结构并优化反应中间体的吸附行为,进而提高活性位点的本征活性。在0.1mol·L^(-1)HCI电解液中,h-PC/Zn_(3)(PO_(4))_(2)/Zn_(2)P_(2)O_(7)在-0.2 V vs.可逆氢电极(RHE)电位下NH_(3)的产率可以达到38.7±1.2μg·h^(-1)·mgcat^(-1),法拉第效率为19.8%±0.9%。此外;h-PC/Zn_(3)(PO_(4))_(2)/Zn_(2)P_(2)O_(7)在0.1 mol·L^(-1)Na_(2)SO_(4)溶液中同样展现出优异的电催化氮气还原合成氨性能,NH_(3)产率及法拉第效率分别为17.1±0.8μg·h^(-1)·mgcat^(-1)和15.g%±0.6%,明显优于PC/Zn_(3)P_(2)、C/ZnO和大多数报道的非贵金属电催化剂。这种优异的性能主要归因于多孔结构有利于传质及多组分活性位点协同效应。此外,我们采用非原位X射线光电子能谱(XPS)、透射电子显微镜(TEM)和X射线衍射(XRD)等表征手段对NRR测试前后h-PC/Zn_(3)(PO_(4))_(2)/Zn_(2)P_(2)O_(7)的组成和结构变化进行了剖析。在反应后检测到了新增的N物种信号,证明催化剂确实发生了氮气还原反应。本研究提供了一种通过同步构建传质通道并耦合不同的活性位点以协同增强NRR活性和选择性的新思路,这对加快绿色制氨工业化具有重大意义。

Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO_(2)-to-formate conversion

Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.

High mass loading NiCo_(2)O_(4) with shell-nanosheet/core-nanocage hierarchical structure for high-rate solid-state hybrid supercapacitors

Rational design of advanced structure for transition metal oxides(TMOs) is attractive for achieving high-performance supercapacitors.However, it is hampered by sluggish reaction kinetics, low mass loading, and volume change upon cycling. Herein, hierarchical Ni Co_(2)O_(4) architectures with 2D-nanosheets-shell and 3D-nanocages-core(2D/3D h-NCO) are directly assembled on nickel foam via a facile one-step way.The 2D nanosheets are in-situ generated from the self-evolution of initial NCO nanospheres. This 2D/3D hierarchical structures ensure fast ion/electron transport and maintain the structural integrity to buffer the volume expansion. The 2D/3D h-NCO electrode with an ultrahigh mass loading(30 mg cm^(-2)) achieves a high areal capacity of 4.65 C cm^(-2)(equivalent to 1.29 mAh cm^(-2)) at a current density of 4 mA cm^(-2), and retains 3.7 C cm^(-2) even at 50 mA cm^(-2). Furthermore, the assembled solid-state hybrid supercapacitor yields a high volumetric energy density of 4.25 mWh cm^(-3) at a power density of 39.3 mW cm^(-3), with a high capacity retention of 92.4% after 5000 cycles. Therefore, this work provides a new insight to constuct hierarchical electrodes for energy storage application.

Magnetic coupling engineered porous dielectric carbon within ultralow filler loading toward tunable and high-performance microwave absorption

Developing microwave absorption(MA)materials with satisfied comprehensive performance is a great challenge for tackling severe electromagnetic pollution.In particular,the magnetic component/carbon hybrids absorbers always suffer from high filler loading.Herein,we propose a feasible strategy to construct hierarchical porous carbon with tightly embedded Ni nanoparticles(Ni@NPC).These highly dispersed Ni nanoparticles produce strong magnetic coupling networks to enhance magnetic loss abilities.Moreover,the interconnected hierarchical dielectric carbon network affords favorable dipolar/interfacial polarization,conduction loss,multiple reflection and scattering.Impressively,with an ultralow filler loading of 5 wt.%,the resultant Ni@NPC/paraffin composite achieves an excellent MA performance with a minimum reflection loss of as high as-72.4 dB and a broad absorption bandwidth of 5.0 GHz.This capability outperforms most current magnetic-dielectric hybrids counterparts.Furthermore,the MA capacity can be easily tuned with adjustments in thickness,content and type of magnetic material.Thus,this work opens up new avenues for the development of high-performance and lightweight MA materials.

Catalytically enhanced thin and uniform TaS2 nanosheets for hydrogen evolution reaction

Though the transition-metal dichalcogenides （TMDs） were proven to have a better performance on the hydrogen evolution reaction （HER）, the bulk production of active TMD materials remains a challenging work. This report overcomes those barriers by showing a simple procedure to synthesize TaS2 nanosheets through modifying the arc discharge process. The usage of chloride as the transporting agent reduces the growth period of the formed TaS2 with active edge sites. TaS2 is found to have a uniform thickness （4 nm） with high crystallinity and adopt a 2H polytype （double-layered hexagonal） structure. The as-synthesized TaS2 has superior activity for HER with the potential of 280 mV.