表面合金电催化剂上甲酸氧化的原位FTIR反射光谱研究

运用原位红外反射光谱(FTIRS)和电化学循环伏安法(CV)研究了甲酸在三种不同电极上的电催化特性。结果表明甲酸在碳载铂电极(Pt/GC)上的电催化氧化机理与本体铂电极(Pt)相类似,即可以通过活性中间体或毒性中间体氧化至CO_2。Pt/GC对甲酸的氧化比Pt具有更高的电催化活性。Pt/GC表面以Sb吸附原子修饰的电极(Sb-Pt/GC)上,甲酸氧化的起始电位(E;)提前至-0.10V,氧化电流峰电位(Ep)提前至0.34V,氧化峰电流(jp)值增加了7.28倍,半峰宽(FWHM)为0.30V。同样,Surface al-loy/GC电极上,E_I为-0.12V,E_p为0.32V和j_p为7.25mA·cm~(-2),相对Pt/GC分别负移了0.22,0.02V和增大了8.15倍,半峰宽(FWHM)为0.5V。表明Sb-Pt/GC和Surface alloy/GC电极不仅能够有效地抑制毒性中间体CO的生成,而且还可以显著地提高其对活性中间体的氧化的电催化活性。     

电化学红外光谱研究铂电极上甲酸分解成CO的反应中桥式吸附甲酸根的作用

采用电化学原位红外光谱技术研究了多晶Pt电极上甲酸的分解反应. 研究发现,在恒电位下(0.4 V vs. RHE)从不含甲酸的支持电解质溶液切换到含甲酸的溶液时,CO_ad的生成速率在切换的最初也就是甲酸根的覆盖度为零最大,切换后的1 s内甲酸根的覆盖度达到平衡,而COad的生成速率逐步降低. E由0.75 V变至0.35 V的电位阶跃实验显示：电位阶跃后的瞬间,甲酸根的红外光谱强度迅速降低,而CO_ad的生成强度随时间缓慢增加. 实验表明甲酸根不是甲酸脱水生成CO的反应活性中间体.     

甲酸在Pt(100)/Sb电极上氧化的时间分辨原位FTIR反射光谱研究

以电化学原位时间分辨ＦＴＩＲ反射光谱和循环伏安方法研究甲酸在不同Ｓｂ覆盖度修饰的Ｐｔ（１００）单晶电极上的氧化。发现Ｓｂａｄ的修饰抑制了甲酸的解离吸附,使反应经活性中间体直接氧化至ＣＯ２。电化学和红外光谱数据表明,θＳｂ＝０．２４的Ｐｔ（１００）／Ｓｂ电极具有最高的电催化活性。     

利用快速扫描伏安法测定醋酸根和甲酸根在铂(111)电极上吸附等温线 (cited: 3)

快速扫描伏安法是一种可以用来区分氧化/还原,吸附/脱附反应的有效工具. 这里,我们将提供一种新的方法,在一种相对浓度较低的反应物溶液中,利用不同的电位扫描速率(相对于扩散速率),可以得到电极表面的吸附/脱附过程的等温线. 本文将以醋酸根在酸性溶液中在Pt(111)上吸附作为例子,并将此方法扩展到复杂的甲酸氧化反应机理研究中.     

超临界水中甲酸分解反应动力学的密度泛函理论研究

采用密度泛函方法(B3LYP)在6-311+g(3df,2p)基组水平上,针对甲酸在超临界水中分解,研究了HCOOH+2H_2O反应和HCOOH+3H_2O反应的微观动力学机理。将理论计算结果与已有的实验结果对比发现,甲酸在超临界水中分解主要通过HCOOH+3H_2O反应机理进行,存在脱羧反应R(HCOOH+3H_2O)→d→TSd/e→e→TSe/P3→P3和脱羰反应R(HCOOH+3H_2O)→f→TSf/P4→P4两条主反应通道。利用传统过渡态理论(TST)计算得到两条主通道速控步骤在650～1500 K温度范围内的速率常数k_3和k_4,其表达式分别为k_3=2.99×10~(12)exp(-169.89 kJ·mol~(-1)/RT)s~(-1)和k_4=3.00×10~9exp(-159.01 kJ·mol~(-1)/RT)s~(-1)。     

正丙醚低温氧化特性的反应机理研究

醚类被认为是优质的直接燃料或燃料添加剂。为进一步揭示醚类的低温氧化反应机制,本文构建了包含详细机理的正丙醚燃烧反应动力学模型,并利用前人的高压氧化实验数据对模型进行了验证。相比于前人的模型,本文模型可以准确预测不同当量比条件下正丙醚的氧化特性。基于模型分析,本文揭示了不同温度下OH自由基的来源以及不同温度下正丙醚的氧化路径差异,为正丙醚的进一步研究提供了方向。     

甲酸在铂钌电极上电催化氧化的原位SERS研究

采用循环伏安法和电化学原位表面增强拉曼光谱(in-situ SERS)技术研究了甲酸在铂钌电极上解离吸附与氧化行为。发现甲酸在铂钌电极上也能自发解离吸附。铂钌电极上CO的氧化峰电位与粗糙铂电极相比负移了180mV,把CO氧化完毕的电极电位亦负移了300 mV,从分子水平证实铂钌电极对甲酸电催化氧化的活性比纯铂电极更高。该研究结果表明,SERS技术可望拓展为研究电催化体系的有效工具。     

甲酸乙酯氧化偶联催化剂的表面特征

用ＴＰＳＲ，ＴＰＤ，ＣＴＰＲ和ＩＴＤ在线分析技术，初步考察了ＨＺＳＭ－５负载型金属氧化物催化剂上甲酸乙酯氧化偶联表面反应性能，以及催化剂表面对氧的吸附能力，对ＣＯ吸附和反应性能，同时，通过ＸＰＳ，ＥＰＲ和ＣＯ－ＩＲ，ＣＯ２－ＩＲ等物理方法，对甲酸乙酯氧化偶联催化剂的表面组成，表面酸碱性及在不同温度下ＣＯ和ＣＯ２在催化剂表面吸附态的变化，进行了初步的探索，研究结果初步揭示，不同载体，不同金属氧化组成     

苯甲酰甲酸热分解分应机理的理论研究

本文用ＡＭ１方法研究了苯甲酰甲酸热分解反应，计算所得活化势垒为１７８．３２９ｋＪ／ｍｏｌ，这与实验值一致。     

钯基双金属合金催化甲酸制氢研究

甲酸具有来源广、成本低、质量储氢密度高等优势，成为潜在的化学储氢载体之一，然而，现在甲酸脱氢技术存在催化剂易失活、产物CO浓度高等挑战。开发高性能甲酸脱氢催化剂并实现脱氢产物的选择性调控是推动甲酸制氢技术长效发展的关键。本文提出以生物炭为载体、含钯双金属合金为活性组分，构筑Pd-M/BC(M=Cu, Ni, Fe, Co;BC为生物炭)催化剂，实现甲酸低温、高转化率及低CO选择性制氢。考察了不同热解温度生物炭载体、活性组分对甲酸脱氢性能的影响，结果表明，150°C、0.006 mL/min甲酸流率下可得到最低的CO选择性(1.31%)与高甲酸转化率(74.88%)，该研究可为Pd-M/BC催化甲酸脱氢技术的发展提供理论指导。     

Ultrathin‐Carbon‐Layer‐Protected PtCu Nanoparticles Encapsulated in Carbon Capsules: A Structure Engineering of the Anode Electrocatalyst for Direct Formic Acid Fuel Cells

Structure engineering is an effective strategy to enhance the performance of electrocatalysts for the formic acid oxidation reaction. However, it remains a challenge to prepare a highly active electrocatalyst based on a distinct understanding of its structure‐dependent performance. The design and synthesis of ultrathin‐carbon‐layer‐protected PtCu nanoparticles (NPs) encapsulated in a N‐doped carbon capsule (PtCu@NCC) is reported. This system is fabricated by using Zn‐based metal–organic frameworks as the carbon support source and metal‐containing tannic acid as the protecting shell template. It displays 9.8‐ and 9.6‐fold enhancements in mass activity and specific activity compared to commercial Pt/C. Moreover, a constructed direct formic acid fuel cell using PtCu@NCC as the anodic electrocatalyst delivers a maximum power density of 121 mW cm^?2. Significantly, PtCu@NCC exhibits superior structural stability and catalytic durability in both half‐cell and full‐cell tests. A mechanism study reveals that the enhanced activity is partially attributed to facilitated electro‐oxidation kinetics of formic acid in the unique structure of PtCu@NCC, while the excellent durability stems from the “protecting effect” of the in‐situ‐formed ultrathin carbon layer on the surface of the PtCu NPs. This work opens a new avenue for the development of high‐performance electrocatalysts for fuel‐cell applications by offering essential insights into the structure–performance relationship of the materials.     

Formic acid decomposition on palladium-coated Pt(1 1 0)

Pt/Pd anode catalysts for direct formic acid polymer electrolyte membrane fuel cells outperform both Pt and Pd in steady-state electrooxidation trials. Temperature-programmed desorption (TPD) experiments in ultra-high vacuum (UHV) were performed with 1 L formic acid on clean Pt(1 1 0), 0.6 monolayers Pd/Pt(1 1 0), and multilayer Pd/Pt(1 1 0) to gain a better understanding of the effect of Pd additions to a Pt catalyst. Both dehydration and dehydrogenation of formic acid occur on all three surfaces. As Pd coverage increases, the activation barrier for formate decomposition to CO₂ decreases, but the effect does not explain the unusual activity of Pt/Pd in the electrochemical environment.     

Temperature programmed desorption study of acetylene on a clean,H-covered,and O-covered Pt(111) surface

The reactions of acetylene on a clean, a H-covered and an O-covered Pt(111) surface were studied by temperature programmed desorption for various coverages of acetylene, and acetylene to H or O ratios. The desorption products were quantitatively determined. On a clean surface, acetylene decomposes to hydrogen and surface carbon. A small amount of self-hydrogenation to ethylene also occurs during decomposition. On a H-covered surface, hydrogenation to CH₄, C₂H₆, and ethylene, and decomposition to hydrogen and surface carbon occur simultaneously. The reactions on these two surfaces can be explained by the presence of two sites. One site is a bare surface Pt atom on which decomposition is the primary reaction pathway. The other site is a Pt atom with adsorbed H on which hydrogenation is the primary reaction pathway. On the O-covered surface, the decomposition reaction takes place together with an oxidation reaction which yields CO, CO₂, and water. The oxidation reaction probably proceeds via an intermediate that has a stoichiometry of CH. Results on the O-covered surface are consistent with the model that oxygen absorbs in islands, and the oxidation reaction takes place at the perimeter of the islands. These results are compared with those of ethylene reaction on the same Pt surfaces.     

Surface (electro-)chemistry on Pt(1 1 1) modified by a Pseudomorphic Pd monolayer

The formic acid and methanol oxidation reaction are studied on Pt(1 1 1) modified by a pseudomorphic Pd monolayer (denoted hereafter as the Pt(1 1 1)-Pd_1 ML system) in 0.1 M HClO₄ solution. The results are compared to the bare Pt(1 1 1) surface. The nature of adsorbed intermediates (CO_ad) and the electrocatalytic properties (the onset of CO₂ formation) were studied by FTIR spectroscopy. The results show that Pd has a unique catalytic activity for HCOOH oxidation, with Pd surface atoms being about four times more active than Pt surface atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO₂ is observed at low potentials. This indicates that the reaction can proceed on Pd at low potentials without the typical “poison” formation. In contrast to its high activity for formic acid oxidation, the Pd film is completely inactive for methanol oxidation. The FTIR spectra show that neither adsorbed CO is formed on the Pd sites nor significant amounts of CO₂ are produced during the electrooxidation of methanol.     

Bimetallic alloy Pt/Ag nanoparticles with enhanced catalytic activity for formic acid oxidation

Here, we report the synthesis of Pt/Ag bimetallic alloy catalyst through combining the ion implantation and electrodeposition method. Ag nanoparticles are employed as the seeds for the growth of Pt nanoparticles. Pt/Ag alloy catalyst demonstrates much higher catalytic activity than pure Pt catalyst, which is about three times more active on the basis of equivalent Pt electrochemically active surface area than that of the pure Pt catalyst. The ion implantation of Ag efficiently enhances the catalytic activity of Pt catalyst for formic acid oxidation.     

Mapping the local reaction kinetics by PEEM: CO oxidation on individual (100)-type grains of Pt foil

The locally-resolved reaction kinetics of CO oxidation on individual (100)-type grains of a polycrystalline Pt foil was monitored in situ using photoemission electron microscopy (PEEM). Reaction-induced surface morphology changes were studied by optical differential interference contrast microscopy and atomic force microscopy (AFM). Regions of high catalytic activity, low activity and bistability in a (p,T)-parameter space were determined, allowing to establish a local kinetic phase diagram for CO oxidation on (100) facets of Pt foil. PEEM observations of the reaction front propagation on Pt(100) domains reveal a high degree of propagation anisotropy both for oxygen and CO fronts on the apparently isotropic Pt(100) surface. The anisotropy vanishes for oxygen fronts at temperatures above 465?K, but is maintained for CO fronts at all temperatures studied, i.e. in the range of 417 to 513?K. A change in the front propagation mechanism is proposed to explain the observed effects.     

Spatiotemporal self-organization in the oscillatory HCOOH oxidation on a Pt ribbon electrode – Theory and experiments

Since the current density near the edges of ribbon and disk electrodes is enhanced, the resulting stationary and non-stationary double layer potential is generally inhomogeneous in all electrochemical reactions. We investigate the impact of this edge effect induced spatial inhomogeneity on the pattern formation of the oscillatory formic acid oxidation on thin Pt ribbon electrodes. In order to be able to theoretically describe the spatiotemporal behavior of the double layer potential distribution, we derive and discuss the properties of the electrochemical ribbon coupling function for various distances of the reference electrode. The resulting reaction–migration equation is analyzed in connection with a chemical model accounting for the specific reaction mechanism of the formic acid oxidation. The interaction of structural inhomogeneity, chemically induced temporal instability and nonlocal spatial coupling due to ion migration gives rise to novel types of spatiotemporal behavior. The results compare favorably with experiments conducted so far, which are presented as well and can be explained within the framework of reaction–migration equations.