甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

在碱性甘油电氧化反应中,利用电化学傅里叶变换衰减全反射谱红外光谱法,研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响.连续操作的径向流动池包括一个位于内反射元件上方50μm的钻孔电极,可实现红外光谱分析.这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法,同时还提供了对复杂反应(如甘油氧化)产物选择性的检测.通过对泵送电解液进行更耗时的定量高效液相色谱分析,结果表明,衰减全反射红外光谱法可快速鉴定产物.在层流条件下,水中使用0.1 M甘油和1 M KOH,流速为5μL min-1时,甘油转化率较高.转化率和选择性取决于催化剂的负载量,负载量又决定了催化剂层的厚度和粗糙度.由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂,因此当负载量最高达210μg cm-2时,甘油转化率为73％且甲酸选择性接近80％.当最低负载量为13μg cm-2时,甘油转化率达到63％,甲酸选择性降至60％,相应地,C2物种(如乙醇酸盐)选择性较高,为8％.因此,只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜,此时才适合进行优质催化剂的筛选.     

Understanding Synergistic Catalysis on Cu-Se Dual Atom Sites via Operando X-ray Absorption Spectroscopy in Oxygen Reduction Reaction

The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N₄ and Se-C₃ active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N₄ moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu₁-N₄) transforms to O*-(Se₁-C₂) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm⁻² in Zn-air battery.     

Light-off Performance of Three-Way Catalysts Before and After Accelerated Aging Test with an Engine-Dynamometer

This study demonstrates the reaction behavior during the purification of model automotive exhaust gases over Pd catalysts before and after thermal degradation. In particular, to investigate the relationship between the Pd state and the reaction behavior of Pd/Al₂O₃ and Pd/CeO₂−ZrO₂ (CZ), operando X-ray absorption spectroscopy measurements were performed during purifying exhaust gases over real and model catalysts mimicking the degradation of Pd particles and CZ supports after accelerated aging tests. The NO reduction activity of the aggregated Pd metal species was as high as that of the highly dispersed Pd species, but hydrocarbon (HC) poisoning was significantly enhanced by the aggregation of Pd metal particles caused by thermal aging. The existence of a three-phase boundary (TPB) between the CZ, the Pd particles, and the gas phase strongly affected the catalytic activity at low temperatures, and the presence of a sufficient TPB facilitated the combustion of unburned HCs owing to the oxygen storage performance of CZ. Thus, the TPB reduced the poisoning of the precious metal surface by HC species at low temperatures. Therefore, the findings of this study will facilitate the development of next-generation gas purification catalysts with high activity and durability.     

实时磁性测试深入理解锂离子电池中的过渡金属催化作用

催化剂由于具有降低电化学过电位和改善动力学条件的能力,在各种储能器件中起着至关重要的作用.在锂离子电池中,首圈放电过程中形成的固体电解质界面膜,通常被认为是一旦形成就稳定不分解的.而在过渡金属的催化下,这种电解质分解衍生的聚合物凝胶状膜(PGF)能可逆地形成和分解.这种过渡金属催化机制可以进行催化储锂,即形成的PGF具...     

XAFS技术在单原子电催化中的应用

X射线吸收精细谱学(XAFS)技术是从20世纪80年代开始逐渐发展起来的一种材料表征技术, 具有对中心吸收原子的局域结构和化学环境敏感的特征, 非常适合表征单原子催化剂. 本文从XAFS技术的原理和特点出发, 深入探讨了该技术在电催化水分解、 燃料电池阴极反应和二氧化碳电化学还原等多个单原子催化应用场景下的独特作用, 并展望了XAFS技术在单原子电催化领域的未来发展与应用前景, 以期为更深入明确的单原子催化剂结构表征和电催化机理描述提供指导.     

Cu-Bound Formates are Main Reaction Intermediates during CO2 Hydrogenation to Methanol over Cu/ZrO2

Cu/ZrO₂ is a promising catalyst for the hydrogenation of CO₂ to methanol. Reaction pathways involving formates or hydroxycarbonyls have been proposed. We show here that three different types of formates can be observed under reaction conditions at 220 °C and 3 bar, one being located on metallic Cu and two others being bound to ZrO₂. The surface concentrations of formates were determined through calibration curves and their reactivity measured during chemical transient experiments. The Cu-bound formate represented only about 7 % of surface formates, but exhibited a higher reactivity and was found to be the only formate that could account for all the production of methanol. Copper is thus not there only to activate H₂, but also bears other crucial intermediates. This work reemphasizes that fully quantitative IR analyses and transient methods are required to unravel the role of surface species.     

Reaction-Induced Metal-Metal Oxide Interactions in Pd-In2O3/ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol

Ternary Pd-In₂O₃/ZrO₂ catalysts exhibit technological potential for CO₂-based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd-In₂O₃/ZrO₂ systems prepared by wet impregnation evolves under CO₂ hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal-metal oxide interaction energetics. The proximity of InPd_x alloy particles decorated by InO_x layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction-induced restructuring in complex CO₂ hydrogenation catalysts and offer insights into the optimal integration of acid-base and redox functions for practical implementation.     

A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In2O3/Al2O3 Catalysts for CO2 Hydrogenation

CO₂ hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In₂O₃ (Palldium on Indium Oxide) catalysts show high CO₂ conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In₂O₃ species dispersed on Al₂O₃ can match the performance of pure Pd/In₂O₃ systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.