稀土钙钛矿型氧化物催化剂上CO低温氧化性能研究

研究了稀土钙钛矿型氧化物La1-xA′xCo1-yBiyO3-δ(A′z=Ba0.2,Sr0.4;y=0,0.2)催化剂上一氧化碳低温氧化反应.XRD结果表明这4个催化剂均为单相立方钙钛矿结构.18O2和CO脉冲实验结果表明Sr掺杂催化剂的晶格氧活动度和反应性比Ba掺杂的强.TPR结果表明Bi的掺杂降低了催化剂的还原温度,提高了催化活性,且Sr取代部分La比Ba取代部分La更有利于增加催化活性.我们认为,Sr.(或Ba)和Bi的掺杂引起的催化活性的提高与氧空位浓度的增加,Co和Bi离子氧化-还原循环的改善以及晶格氧活动度的增加密切相关.     

钙钛矿型La_((1 x)/2)Sr_((1-x)/2)Co_(1-x)Cu_xO_3催化CO氧化活性与表征

研究了钙钛矿型LaSrCoCu_xO_3催化剂对CO氧化反应的催化活性及其表面氧的催化作用．结果表明，x＝0．4的催化剂对CO氧化具有最高催化活性，常压及本实验条件下CO完全氧化的最低温度为168℃；催化剂均为氧缺陷化合物，吸附于表面晶格氧缺陷上的吸附氧是CO氧化反应的活性氧物种；并发现催化剂中存在有非常价态的C04 ，认为CO氧化反应是通过吸附氧调变Co3 和Co4 价态而进行．     

具有高效析氧催化性能的铁基双元金属有机框架纳米棒研究

析氧反应(OER)是电解水制氢的关键步骤,开发高效、稳定、廉价的OER电催化剂是目前该领域的研究热点.碱性电解液中的OER电催化剂成分以Mn、Fe、Co、Ni等为主,其中单一组分的Fe基化合物催化活性不高,但碱性电解液中的痕量铁杂质极易掺入Ni、Co等非Fe基材料的结构中,极大影响其OER催化性能,即现有大部分非Fe基化合物无法回避Fe的影响.为探究Fe基多金属电催化剂的活性规律,本文以结构清晰、组分可控的Fe基金属有机框架材料为基底,通过掺入Mn、Co、Ni等元素构建双元金属化合物Fe2M-MIL-88B(M=Mn,Co,Ni),并围绕上述Fe基双金属电催化剂的构效关系展开研究.扫描电镜、透射电镜、X射线衍射光谱、红外光谱等表征结果表明,所制备的Fe基双金属材料均为具有MIL-88B构型的纳米棒,其特征三核金属簇Fe₃O中的一个铁原子被第二元金属所替代,从而形成相应的三核混合金属簇Fe₂MO.上述Fe基双金属催化剂的析氧催化活性顺序为:Fe2Ni>Fe₂Co>Fe₂Mn>Fe(0.1 M KOH电解液).其中,Fe₂Ni-MIL-88B电催化剂在10 mA cm^-2析氧电流对应的过电位仅需307 mV,明显低于OER基准电催化剂20 wt%Ir/C(376 mV).结合材料的元素组成、电化学活性比表面积(ECSA)及金属价态分析发现,第二元金属的引入会在不同程度上降低Fe的价态,其中Ni的影响程度最大,Co次之,Mn的影响最小.借助分子轨道理论对上述实验现象进行了解释.处于低自旋态的Ni²⁺与邻近桥氧O^2-之间存在电子排斥作用,因此部分电子将从Ni²⁺经O^2-转移至高自旋态的Fe³⁺,从而在Ni²⁺和Fe³⁺之间形成了较强的电子耦合作用.Co²⁺具有和Ni²⁺相似的构型,但影响稍小.而Mn²⁺和Fe³⁺同为高自旋态,对Fe³⁺的电子结构影响最小,导致活性改善程度最低.密度泛函理论计算得到的自旋态变化情况印证了上述推测.该系列Fe基双金属材料的催化性能主要受金属活性位点的电子结构影响,Fe与邻近金属间形成的电子耦合作用修饰了金属活性位点的电子结构,从而提高了材料的OER本征催化活性.     

La0.7Sr0.3Co1-xFexO3催化剂氮氧化物储存及抗硫性能

采用溶胶-凝胶法通过在静态空气中700°C焙烧制备了不同Fe掺杂量的La0.7Sr0.3Co1-xFexO3(x=0,0.2,0.6,1.0)系列钙钛矿催化剂.考察了Fe掺杂量对催化剂的结构、氮氧化物储存、抗硫及再生性能的影响.研究结果表明:在La0.7Sr0.3CoO3钙钛矿B位用Fe部分取代Co,可有效提高SrCO3物相的分散,X射线衍射(XRD)结果显示样品中基本为钙钛矿物相.随着Fe掺杂量的增加,催化剂的NOx储存量(NSC)下降.对预硫化样品进行NOx储存测试,发现La0.7Sr0.3CoO3催化剂由于表面沉积了硫酸盐,同时钙钛矿结构也遭到了部分破坏,使得NOx储存量和NO氧化能力均大幅度下降,NOx储存量下降了64.2%,NO-to-NO2转化率从72.8%降至43.4%.掺杂Fe元素后,催化剂的抗硫性能都有不同程度的提高,特别是Fe掺杂量为60%的样品具有最佳的抗硫性能和可再生性能.与新鲜样品相比较,再生后样品的NOx储存量仅下降16.6%,而NO-to-NO2转化率为69.1%,几乎与新鲜样品相同.     

Fe/ZrO_2催化剂的Mssbauer谱及XAFS表征

考察了经不同温度还原的Fe/ZrO2 催化剂在CO2 加氢制低碳烃反应中的催化活性 ,最佳结果为CO2 转化率2 7 0 % ,对C2 + 烃的选择性 5 6 7% .采用XRD ,57FeM ssbauer谱 ,FeK 吸收边的X射线吸收近边结构 (XANES)及扩展X射线吸收精细结构 (EXAFS)等表征方法研究了催化剂的表面结构 .结果表明 ,在ZrO2 表面上主要存在α Fe及配位不饱和的Fe3 + 两种物种 .催化剂表面明显呈氧缺位、零价铁相对富集的状态 .还原温度对表面结构有显著的影响 ,最佳还原温度与表面Fe O键的键长有关 .结合这种催化剂在CO2 加氢制低碳烃反应中的催化活性 ,认为α Fe与配位不饱和的Fe3 + 物种的协同作用是其具有较高催化活性的重要原因     

CoBx/Co3O4电催化剂的制备及其氧析出性能

采用NaBH4溶液处理经水热、热处理步骤制得Co3O4纳米棒,得到表面富含氧空位以及无定型CoBx的Co3O4(CoBx/Co3O4)氧析出(OER)电催化剂。利用X射线衍射(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)、X射线光电子能谱仪(XPS)等技术表征了催化剂的物相、微观形貌、元素组成以及表面化学键结构等。通过电化学工作站测试了电极材料的OER活性、稳定性、电化学阻抗等。结果表明,经NaBH4处理后,Co3O4表面高价态Co被还原至低价态Co,最终其表面有无定型CoBx的生成,并含有大量氧空位,有效提升了OER性能。在1.0 mol·L^-1 KOH电解质溶液中,达到10 mA·cm^-2的电流密度时,CoBx/Co3O4所需的过电位由Co3O4的346 mV降至298 mV。     

钙钛矿型复合氧化物在甲烷部分氧化反应中催化性能的研究

自 1 990年以来 ,由甲烷部分氧化制合成气 ( POM)的反应作为对传统甲烷水蒸气重整反应的一个重大改进而受到高度重视 [1] .目前 ,在 POM反应中 ,研究较多的催化剂体系大致可分为贵金属 ( Pt,Pd,Rh,Ru及 Ir) [2 ,3] 以及以 Ni和 Co为主的 B族过渡金属催化剂[4～ 6 ] .最近 ,Hayakawa等 [7,8] 报道了具有钙钛矿结构的复合氧化物 Ca1- x Srx Ti1- y My O3-δ( M=Cr,Fe,Co或 Ni)在甲烷部分氧化制合成气反应中具有一定的催化活性 .本文以本组开发的钙钛矿型复合氧化物 Ba0 .5Sr0 .5Co0 .8Fe0 .2 O3-δ(简称BSCFO)和 Ba0 .5Sr0 .5…     

无定形氧化铁层在纳米多孔BiVO4的光电化学分解水反应中的作用

通过"人工光合成"过程,将太阳能转化成氢能的形式加以存储和利用,是替代传统化石能源的清洁能源的制备有效途径.其中,光电化学分解水是氢能制备的最有潜力的路径之一.n型BiVO4由于具有丰富的储量、较窄的带隙以及合适的能带位置,被称为光电化学领域的研究热点.然而,未修饰的BiVO4光阳极性能并不理想,主要原因在于载流子复合严重、导电性差以及表面催化动力学低等性质的制约.科研工作者们针对这些方面已进行了非常多的研究,例如与电子传输层的复合、产氧电催化剂的担载以及异质结的构建等.其中表面动力学和电荷分离的同时提升是更理想的改善BiVO4光阳极性能的方法.我们在上述研究基础上,采用光化学沉积法在纳米多孔BiVO4电极表面担载无定形氧化铁层,将电极在1.23 V vs.RHE电位下的光电流提升至2.52 mA/cm2,是初始光电化学性能的3倍.采用间歇光照计时电流(i-t)测试,电化学交流阻抗谱(EIS),X射线光电子能谱(XPS),原位和非原位的X射线精细结构能谱(in-situ and ex-situ XAFS)等表征手段研究了无定形氧化铁层的成分和光电化学反应过程中的价态变化,从而分析出光电化学性能提升的原因.间歇光照i-t测试和EIS测试结果表明,无定形氧化铁沉积在BiVO4使电荷累积减少,复合率降低.XPS测试结果发现无定形氧化铁层存在少量的二价铁成分.通过原位XAFS测试发现,BiVO4/FeOx电极中Fe原子的价态在光照和施加外加偏压条件下会有价态的升高,而撤去光照和偏压后Fe原子的价态状态与最初非原位的测试结果重合.这样的结果证明了无定型氧化铁层在光电化学反应过程中由于二价铁成分的存在,能够很好的通过价态改变实现空穴的吸附和传输,即吸附空穴,被空穴氧化成三价或四价,同时结合自身电催化活性,促进表面分解水反应的进行.而水的氧化反应结束时,则伴随着二价铁离子的再生成.这种反应机理为开发更高效的电催化剂,匹配光电极使用,有着重大的指导意义.     

掺杂纳米TiO2光催化性能的研究

利用浸渍法分别制备了Cr、Mn、Fe、Co、Ni、Cu六种过渡金属离子掺杂改性的二氧化钛光催化剂，以乙酸水溶液的光催化氧化反应和二氧化碳还原反应为探针,评价了掺杂催化剂的光催化性能.借助光电子能谱（XPS）、X射线衍射分析（XRD）等手段对掺杂催化剂进行了表征.研究结果表明，经过渡金属离子掺杂后，光催化性能均有不同程度的改善，改善程度按Cr、Co、Ni、Fe、Mn、Cu递增.掺杂后催化剂表面吸附氧的活泼性、金属离子的价态及得电子能力上的差异决定了不同离子掺杂纳米二氧化钛光催化性能的差异.     

掺杂型稀土双钙钛矿光催化剂La2FeTiO6葡萄糖络合法制备与表征

采用葡萄糖络合法制备了双钙钛矿型催化剂La2FeTiO6,进行不同量Sr掺杂改性。利用X射线粉末衍射(XRD)、H2-程序升温还原(H2-TPR)、比表面(BET)、扫描电镜(SEM)、磁性与电性测试等手段对其进行表征,以可见光催化降解对氯苯酚为探针讨论了Sr掺杂对La2FeTiO6催化剂的物理化学性质及可见光催化活性的影响。结果表明:催化剂La2FeTiO6在掺杂Sr后,催化剂的可见光催化活性均有所提高,其中Sr掺杂量为0.08时,催化剂的光催化活性提高最大,光照1 h时对氯苯酚的降解率就已经达到了90%,5 h后降解率达到99.2%。La2FeTiO6通过Sr掺杂改性后光照5 h降解率提高了37.1%。比表面测试和程序升温还原试验结果表明,碱土金属Sr的掺杂提高了催化剂的比表面,促进了双钙钛矿La2FeTiO6中Fe的还原,使其还原峰面积增大,还原温度也有所降低。电性和磁性测量结果说明,碱土金属Sr的掺杂明显影响其催化剂的电磁性能。     

Nickel-iron borate coated nickel-iron boride hybrid for highly stable and active oxygen evolution electrocatalysis

The development of efficient and cost-effective electrocatalysts toward anodic oxygen evolution reaction (OER) is crucial for the commercial application of electrochemical water splitting. As the most promising electrocatalysts, the OER performances of nickel-iron-based materials can be further improved by introducing metalloid elements to modify their electron structures. Herein, we developed an efficient hybrid electrocatalyst with nickel-iron boride (NiFeB) as core and amorphous nickel-iron borate (NiFeB_i) as shell (NiFeB@NiFeB_i) via a simple aqueous reduction. The obtained NiFeB@NiFeB_i exhibits a small overpotential of 237 mV at 10 mA/cm² and Tafel slope of 57.65 mV/dec in 1.0 mol/L KOH, outperforming most of the documented precious-metal-free based electrocatalysts. Benefiting from the in situ formed amorphous NiFeBi layer, it shows excellent stability toward the oxygen evolution reaction (OER). These findings might provide a new way to design advanced precious-metal-free electrocatalysts for OER and the application of electrochemical water splitting.     

A novel ball-in-ball hollow oxygen-incorporating cobalt sulfide spheres as high-efficient electrocatalyst for oxygen evolution reaction

Transition-metal chalcogenides with hollow nanostructure,especially cobalt sulfides,are considered as the most pro mising non-precious metal catalysts for oxygen evolution reactio n.However,it is difficult to synthesize oxygen-containing cobalt sulphides with hollow structure due to the different physical/chemical properties between metal sulfides and metal cobalts.Herein,we report a novel oxygencontaining amorphous cobalt sulfide ball-in-ball hollow sphere s(Co-S-O BBHS) synthesized by an anion exchange method.Taking advantage of the ball-in-ball hollow structure,the amorphous Co-S-O BBHS shows supe rior oxygen evolution reaction(OER) electrocatalytic performance with a low overpotentiat of285 mV at 10 mA/cm~2,small Tafel slope of 49.67 mV/dec,high Faraday efficiency of 96%,and satisfied durability.Experiments and DFT calculations demonstrate that the introduction of oxygen and sulfur modulates the electronic structure of Co-S-O BBHS,thus enhancing the adsorption of *0(adsorbed 0 species on catalyst surface) intermediate,which greatly boosts the catalytic activity towards OER.This work provides a new strategy for controllable synthe sis of complex hollow structures of transition-metal chalcogenides for OER.     

非晶非贵金属催化剂的研究进展及展望

近年来电解水产氢作为一种具有前景的制备及储存可再生能源的方法受到了各界的广泛关注.在此过程中,电解水催化剂是提高能源转换效率的关键.优秀的催化剂应具备高催化活性、高稳定性、低成本以及可大规模生产等性质.科研工作者对电解水的两部分反应,即析氢反应以及析氧反应均进行了广泛及深入的研究.目前,贵金属催化剂,如铂基、钌基催化剂的催化活性要高于其他元素催化剂,但由于其价格昂贵,储量较少使得贵金属催化剂无法得到大规模应用,因此发展非贵金属催化剂对绿色能源的发展具有重要意义.一般而言,催化剂的结晶度越高,其催化活性越好,而近年来非晶催化剂以其更高的催化活性位密度也越来越受到人们的重视.同时,非晶催化剂的成分更加灵活,相比晶体催化剂来说非晶催化剂可以在更大范围内对成分进行调节.此外,非晶催化剂的制备通常都在较为温和的反应条件下进行,这也能够降低生成成本,促进其工业化发展.在这篇综述里我们介绍了电解水反应的基本原理,总结了近期非晶析氢、析氧以及双功能催化剂的研究进展.并随后探讨了电解水反应目前的难点并对非晶催化剂的制备进行了展望.     

析氧反应中催化剂-电解质界面的质子动力学研究

电催化水分解是一种可持续的绿色产氢技术,该技术在工业化的大规模应用急需开发高效稳定的非贵金属催化剂,用于提高析氧反应(OER)的反应速率.研究发现,钙钛矿氧化物是优异的OER催化剂,但是对于发生在催化剂-电解质固液界面上的反应机理仍有争论.目前普遍认为,在OER反应过程中,水分子吸附在金属氧化物催化剂表面的金属活性中心...     

Water-Assisted Chemical Route Towards the Oxygen Evolution Reaction at the Hydrated (110) Ruthenium Oxide Surface: Heterogeneous Catalysis via DFT-MD and Metadynamics Simulations

Notwithstanding that RuO₂ is a promising catalyst for the oxygen evolution reaction (OER), a plethora of fundamental details on its catalytic properties are still elusive, severely limiting its large-scale deployment. It is also established experimentally that corrosion and wettability of metal oxides can, in fact, enhance the catalytic activity for OER owing to the formation of a hydrated surface layer. However, the mechanistic interplay between surface wettability, interfacial water dynamics and OER across RuO₂, and what degree these processes are correlated are still debated. Herein, spin-polarized Density Functional Theory Molecular Dynamics (DFT-MD) simulations, coupled with advanced enhanced sampling methods in the well-tempered metadynamics framework, are applied to gain a global understanding of RuO₂ aqueous interface (explicit water solvent) in catalyzing the OER, and hence possibly help in the design of novel catalysts in the context of photochemical water oxidation. The present study quantitatively assesses the free-energy barriers behind the OER at the (110)-RuO₂ catalyst surface revealing plausible pathways composing the reaction network of the O₂ evolution. In particular, OER is investigated at room temperature when such a surface is exposed to both gas-phase and liquid-phase water. Albeit a unique efficient pathway has been identified in the gas-phase OER, a surprisingly lowest-free-energy-requiring reaction route is possible when (110)-RuO₂ is in contact with explicit liquid water. By estimating the free-energy surfaces associated to these processes, we reveal a noticeable water-assisted OER mechanism which involves a crucial proton-transfer-step assisted by the local water environment. These findings pave the way toward the systematic usage of DFT-MD coupled with metadynamics techniques for the fine assessment of the activity of catalysts, considering finite-temperature and explicit-solvent effects.     

Scaled‐Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution Catalysis

The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co‐precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self‐reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm^?2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale‐up production of amorphous metal oxides for high‐performance OER catalysts.     

Substituent position effect of Co porphyrin on oxygen electrocatalysis

Substituent effect of metal porphyrin molecular catalysts plays a crucial role in determining the catalytic activity of oxygen electrocatalysis. Herein, substituent position effect of Co porphyrins on oxygen electrocatalysis, including the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), was investigated. Two Co porphyrins, namely 2,4,6-OMe-CoP and 3,4,5-OMe-CoP, were selected as the research objects. The ORR and OER performance was evaluated by drop-coating molecular catalysts on carbon nanotubes (CNTs). The resulted 3,4,5-OMe-CoP/CNT exhibited high bifunctional electrocatalytic activities and better long-term stability for both ORR and OER than 2,4,6-OMe-CoP/CNT. Furthermore, when applied in the Zn-air battery, 3,4,5-OMe-CoP/CNT exhibited comparable performance to that with precious metal-based materials. The enhanced catalytic activity may be attributed to the improved charge transfer rate, mass transfer and hydrophilicity. This work provides an effective strategy to further enhance catalytic activity by introducing substituent position effect, which is of great importance for developing more efficient energy-related electrocatalysts.     

金属-有机框架原位转化合成无定形Fe基双金属氢氧化物催化剂催化析氧反应性能

传统化石能源的大量消耗使得能源短缺和环境污染等问题日益严峻.社会的可持续发展需要进行能源结构调整,寻求清洁、可再生的替代能源已迫在眉睫.氢能作为一种可再生能源,其热值高,燃烧产物无污染,是未来最理想的能源形式之一.水裂解制氢是公认的未来清洁制氢的一种有效途径.然而,无论是电催化或光催化水裂解反应,析氧反应都是关键的半反应.因其复杂的四电子过程导致动力学缓慢,使得析氧半反应成为水裂解反应的瓶颈.长久以来,贵金属Ir和Ru基材料是被广泛研究的高活性的析氧催化剂.然而高成本和低储量极大地限制了它们的大规模工业化应用.因此,开发高效、储量丰富的析氧催化剂,意义重大但仍充满挑战性.本文考察了一种简便而有效的合成策略,在碱性水溶液条件下,成功实现将一系列Fe基金属有机框架(MOF)前驱物原位转化为无定形Fe基双金属氢氧化物纳米结构.这些由MOF前驱物转化得到的氢氧化物纳米结构保留了前驱体纳米棒的宏观形貌,由许多超细的无定形纳米颗粒(平均粒径小于10 nm)构成,在催化反应中可以提供丰富的催化活性位,相邻的纳米颗粒之间紧密接触,有利于电子在催化活性位之间传递.以玻碳电极作为基底,通过组分优化得到的NiFe-OH-0.75催化剂样品在电催化析氧反应中仅需270 mV的过电位便可达到10 mA cm^-2的电流密度,Tafel斜率为39 mV dec^-1.将催化剂负载到三维泡沫镍基底上时,由于电极基底导电性提升以及传质增加,在10 mA cm^?2的电流密度所需的过电位可以降低到235 mV,Tafel斜率为37 mV dec^?1,并且表现出较好的稳定性.同时,本文进一步证实这些无定形氢氧化物可以用作助催化剂,与合适的光敏剂结合,实现有效的光催化水氧化反应.在KH2PO4-K2HPO4缓冲溶液(pH=9)体系中,以[Ru(2,2’-bipyridine)3]Cl₂为光敏剂,Na2S2O8为电子受体,由CoFe-MIL-0.75前驱体转化所得到的CoFe-OH-0.75助催化剂表现出更优越的光催化产氧性能,产氧效率可达59.6%.本文结果可以为其他基于MOF及其相关衍生材料的制备提供新思路.     

Advances in understanding the role of surface hole formation in heterogeneous water oxidation

The electrochemical oxidation of water to molecular oxygen, that is, the oxygen evolution reaction (OER), is a key anodic reaction that supplies electrons and protons for many technologically interesting reduction processes, such as carbon dioxide reduction and nitrogen fixation. Because the OER is a slow reaction, it needs to be facilitated by (photo)electrocatalysts. To develop such catalysts, advances in the mechanistic understanding of the OER are critical. In this opinion, we focus on a key aspect of the OER, namely, how the accumulation of oxidative charge (‘holes’) on the surface of a catalyst triggers O ? O bond formation. We discuss recent advances in understanding the factors that drive surface hole formation at specific sites.