泡沫镍负载二维金属有机框架及其衍生物耦合阵列用于高活性双效氧电极

氧电催化一般涉及到氧还原反应(ORR)和氧析出应(OER),是诸如燃料电池,金属空气电池和水电解池等能源转换与存储技术的关键步骤.其中,可充电的金属锌空气电池具有较高的能量密度,开发成本较低,运行安全且环境友好.然而,开发并采用高效,低成本且储量丰富的催化材料代替贵金属基电催化剂,仍旧是现阶段尚未完全解决的问题和挑战.最近,金属有机框架(MOFs)以及碳基的金属有机框架衍生物作为高效电催化剂,因其超乎寻常的形貌,结构,组分和功能性的可调节能力,已经逐渐引起了广泛的关注和研究兴趣.因此,本文报道了一种泡沫镍负载的二维金属有机框架及其衍生物耦合阵列作为无粘结剂型ORR/OER双效催化剂,能够实现高比表面积,高电导率和高双功能性,同时避免了使用有机粘结剂的复杂制备过程和不可避免的电池性能影响.与传统设计不同,本文主要通过集成各司其职的不同功能组分并充分暴露电化学活性面积来提高双效电极的整体活性.电化学测试结果表明,耦合阵列电极(R-NCM)相比于MOFs阵列(NCM)和MOFs衍生物阵列(A-NCM)等对比电极,具有显著提高的双效氧电极性能,氧还原反应的起峰电位约为0.90 V,而氧析出反应电流密度达到100 m Acm-2时的过电势为319 m V.由于其在生长–热裂解–再生长过程中所具有的稳定的站立多级二维纳米片结构,所制备的双效氧电极材料表现出显著增强的双官能团性,电化学活性面积,反应动力学和稳定性,并可进一步用于可充电的金属锌空气电池(ZABs).考虑到制备过程的可行性与简洁性,所提出的生长–热裂解–再生长策略不仅能够用于耦合型分级纳米片阵列结构的合成,还能为设计开发相关能源电化学装置的高活性电极结构提供借鉴.

Pd单原子/团簇高效催化铃木偶联反应

铃木偶联反应是合成聚烯烃、苯乙烯和联苯衍生物等功能性有机化合物的有力工具,广泛应用于精细化工、制药和生化工业领域.钯(Pd)基催化剂是目前性能最好的铃木偶联反应催化剂,但钯的低丰度和高成本限制了其大规模应用.因此,提高Pd原子的利用效率,降低Pd用量至关重要.减小金属纳米粒子的尺寸,使其成为小团簇甚至孤立的金属原子是实现金属原子高利用率的有效方法之一.此外,与纳米晶体相比,高度分散的Pd原子和具有低配位和不饱和构型的亚纳米团簇可能会导致催化活性位点数量增加,进而提升Pd基催化剂的性能.然而,高表面自由能使得合成高度分散的Pd单原子和亚纳米团簇变得困难,因此,如何制备具有优异铃木偶联反应催化性能的Pd单原子/团簇催化剂是一个极具挑战性的课题.本文开发了一种溶液快速退火(SRA)工艺来稳定氮掺杂介孔碳负载的Pd单原子/团簇(Pd/NMC),制得的催化剂表现出较好的催化铃木偶联反应性能.透射电子显微镜结果表明,所制Pd/NMC催化剂中Pd以单原子和小金属团簇(粒径为0.3-1.1 nm)的形式高度分散在氮掺杂介孔碳载体的表面;X射线衍射结果表明,该催化剂没有与Pd相关的衍射峰,进一步证明了Pd以单原子和小金属团簇,而非纳米晶的形式存在.这得益于SRA工艺创造的不平衡热条件,抑制了Pd原子的团聚,提高了Pd原子在载体表面的分散性.与商业Pd/C催化剂相比,Pd/NMC催化剂对氯苯的铃木偶联反应表现出更好的催化性能(100%的选择性和95%的产率)和稳定性(循环使用10次后活性几乎没有衰减),此外对其他衍生物底物同样表现出较好的催化性能.第一性原理计算表明,在Pd(111)上联苯解吸的吉布斯自由能为3.24 eV,显著高于Pd_(1)/NMC(0.72 eV)和Pd_(13)/NMC(1.31 eV),在理论上同样证明了与Pd纳米颗粒相比,Pd单原子/团簇催化剂更有利于反应物的转化.此外,本文新开发的前驱体SRA工艺可被用作稳定金属团簇(例如Pd、Pt、Ru)的通用方法,为构建高效、高度分散的金属原子和亚纳米团簇催化剂提供了新的可能性.

Unveiling the intrinsic properties of single NiZnFeO_x entity for promoting electrocatalytic oxygen evolution

Although considerable research efforts have been devoted to the design and development of non-noble electrocatalysts for oxygen evolution reaction(OER), substantial enhancement of OER performance with commercial-scale water electrolysis remains a big challenge. This could result from the difficulties in detecting the intrinsic properties and overlooking the assembly process for electrochemical OER process. Here, we employ a microjet collision method to investigate the intrinsic OER activities of individual NiZnFeO_x entities with and without a moderate magnetic field. Our results demonstrate that single NiZnFeO_x nanoparticles(NPs) show the excellent OER performance with a lowest onset potential(~1.35 V vs. RHE) and a greatest magnetic enhancement(~118%) among bulk materials, single agglomerations and NPs. Furthermore, we explore the utility of theoretical investigation by density functional theory(DFT)calculations for studying OER process on NiZnFeO_x surfaces without and with spin alignment, indicating monodispersed NiZnFeO_xNPs with totally spin alignment facilitates the OER process under the external magnetic field. It is found that the well-dispersion of NiZnFeO_x NPs would increase the electrical conductivity and the surface spin state, resulting in promoting their OER activities. This work provides a test for uncovering the essential roles of NPs assembly to a significant promotion of their magnet-assisted OER.

Oxygen-deficient metal oxides:Synthesis routes and applications in energy and environment

Oxyge n vaca ncies impla ntation is an efficie nt way to adjust the physical and chemical properties of metal oxide nano materials to meet the requirements for particular applications.Through reasonable defects design,oxyge-deficient metal oxides with excellent optical and electrical properties are widely applied for environmental protection and energy uses.This review discusses recent advances in synthetic approaches of oxygervdeficient metal oxides and their applications in photocatalysis,electrocatalysis,and energy storage devices.The perspectives of oxyge n?deficie nt metal oxides for increased en ergy dema nd and en vironme ntal sustai liability are also exami ned.

NiPS_(3)quantum sheets modified nitrogen-doped mesoporous carbon with boosted bifunctional oxygen electrocatalytic performance

Electrocatalysts for oxygen reduction reactions(ORR)and oxygen evolution reactions(OER)are highly crucial and challenging toward the energy storage and conversion technologies such as fuel cells,metal-air batteries and water electrolysis.To replace noble-metal based catalysts and boost catalytic performance of carbon-based materials,we initially develop the nickel,phospho rus,sulfur and nitrogen co-modified mesoporous carbon(NiPS_(3)@NMC)as a bifunctional oxygen electrocatalyst.The perfo rmance for ORR(half-wave potential at 0.90 V)and OER(10 mA cm^(-2)at 1.48 V)surpasses those of Pt/C coupled with IrO_(2)catalysts and most of the non-precious metal based bifunctional electrocatalysts reported in related literature.Moreover,the electrochemical durability is also confirmed by accelerated durability tests(ADTs)and long-term chronoamperometry(CA)tests.We demonstrated that the interfacial effect between NiPS_(3)quantum sheets(QS s)and NMC substrates by thermal activation contributed to the enhanced oxygen electrode bifunctionality with more active sites,due to the electrons-donating from nickel,phosphorus and sulfur elements and relatively enriched pyridinic type N.Such excellent overall performance highlights the potential application of NiPS3 QSs and NMC composites as the materials on energy conversion and storage.

Aerodynamic levitated laser annealing method to defective titanium dioxide with enhanced photocatalytic performance

Defective TiO2 has attracted increasing attention for use in photocatalytic and electrochemical materials because of its narrowed band-gap and improved visible-light photocatalytic activity. However, a facile and efficient approach for obtaining defect-rich TiO2 still remains a challenge. Herein, we demonstrate such an approach to narrow its bandgap and improve visible-light absorption through implanting abundant defects by aerodynamic levitated laser annealing （ALLA） treatment. Note that the ALLA method not only provides rapid annealing, solidifying and cooling process, but also exhibits high efficiency for homogeneous and defective TiO2 nanoparticles. The laser-annealed TiO2 achieves a high hydrogen evolution rate of 8.54 mmol.h-1.g-1, excellent decomposition properties within 60 min, and outstanding recyclability and stability, all of which are superior to the corresponding properties of commercial P25.