可逆与不可逆吸附氢在合成甲醇反应中的作用

在自行设计和建立的加压动态分析装置上研究了合成甲醇催化剂上氢的吸附和反应行为。结果表明:在反应条件下催化剂上吸附的氢可分为可逆吸附氢和不可逆吸附氢;不可逆吸附氢又可分为能被CO顶替出来的和不能被CO顶替出来的两部分;能被CO顶替出来的不可逆吸附氢对CO的吸附起促进作用,不能被CO顶替出来的不可逆吸附氢是合成甲醇催化剂必不可少的“组分”或称“促进剂”;同时甲醇的生成是可逆吸附氢与一氧化碳作用的结果。     

镍铝催化剂吸附动力学参数的非线性动态分析

在推导出适应于甲烷化反应体系非线性动态分析不同吸附物种动力学参数模型的基础上，采用计算优化出工业镍铝甲烷化催化剂上可逆吸附氢和可逆吸附一氧化碳的吸附速率常数和吸附平衡常数。结果表明，镍铝催化剂上吸附可逆氢要比吸附一氧化碳快２．２倍左右。该结果为镍铝催化剂上甲烷化产物的生成主要依赖于一氧化碳的吸附这一判断提供了理论依据。由于镍铝催化剂上甲烷化是可逆吸附氢与不可逆吸附一氧化碳共同作用的结果，且不可逆吸     

脉冲氧化亚氮-色谱法测定含铜催化剂的活性表面积

根据氧化亚氮在表面零价铜上分解放出氮的特征反应,建立了脉冲氧化亚氮-色谱法测定各种含铜催化剂活性表面积的方法。对商品氧化铜、实验室中碳酸钠分解硝酸铜所制成的活性氧化铜、Raney 铜、工业脱氧铜催化剂、一氧化碳加氢低压合成甲醇ICI-51型催化剂以及目前正在开发的合金铜-锌催化剂等均进行了活性铜表面积的测量。结果表明,上述催化剂的活性表面积仅占总表面积的一部分,甚至是极少的一部分。约为3—30%。将一系列合金铜锌催化剂的活性表面积数值与其在实验室中一氧化碳加氢合成甲醇的催化活性进行关联,发现甲醇时空收率与催化剂的活性夜面积成正比,亦即反应速度与活性表面积呈线性关系。通过对催化剂表面铜使氧化亚氮分解并吸附氧的本质的探讨,证实了一个氧原子吸附在两个相邻的表面铜原子上的设想,为含铜催化剂对一氧化碳加氢合成甲醇反应活性组分问题的探讨提供了有用的信息。     

CO在Ni-Zn/C催化剂上的可逆吸附

ＣＯ在ＮｉＺｎ／Ｃ催化剂上的可逆吸附彭峰黄仲涛（华南理工大学化学工程系，广州５１０６４１）关键词一氧化碳，可逆吸附，吸附热，镍，锌，活性炭，负载型催化剂分类号Ｏ６４３／Ｏ６４７化学吸附是分子与催化剂表面原子间形成吸附化学键，具有选择性，是多相催化...     

甲醇在Pd-La2O3/SiO2催化剂的程序升温脱附和分解及D2O吸附的影响

用质谱检测的程序升温脱附技术研究了甲醇在Pd-La_2O_3/SiO_2催化剂上的脱附和分解行为,高温He处理过的催化剂基本上不吸附氢,但对甲醇分解仍有一定的活性和较高的选择性。H_2还原后的催化剂有较大的吸附氢的能力,对甲醇分解的活性也较高,但分解产物中CO_2的含量明显增加,LaO的助催化作用主要是提高催化剂表面甲醇吸附物类的浓度和减弱CO的吸附强度,并因此抑制它的歧化反应。 DO对吸附实验表明甲醇在催化剂表面的吸附有可逆和不可逆两种形式,对于可逆吸附的甲醇,其后DO对吸附所引起的置换效应尤为明显。     

可逆与不可逆氢的在甲烷化反应中的作用

用自行设计和建立的加压动态分析装置研究了甲烷化催化剂上氢的吸附和反应行为。结果表明，在反应条件下吸附和氢可区分为不可逆吸附氢和可逆吸附氢两类，不可逆吸附氢又可分为能被ＣＯ顶替出来的和不能被顶替的两种。起甲烷化反应的是可逆吸附氢，而能被ＣＯ顶替出来的不可逆氢对吸附ＣＯ起促进作用，不能被ＣＯ顶替出来的不可逆氢是甲烷化催化剂必不可少的组分（或称“促进剂”）。     

可逆与不可逆吸附CO在合成甲醇反应中的作用

合成甲醇反应是CO+H_2反应系列中较简单的反应之一,它与同系列的甲烷化反应有着不同的反应条件.从热力学观点来看,甲烷化反应和合成甲醇反应同是体积缩小反应,加压应该有利于两反应的进行,实际上合成甲醇反应需加压,而甲烷化反应却不一定需要加压.最近我们用动态分析技术对烃的临氢转化、乙炔加氢和苯加氢反应研究发现,在实际反应条件下,反应物在催化剂表面上的吸附可分为可逆与不可逆吸附两类,它们在多相催化反应中对活性、选择性和稳定性均有影响,但是它们对操作压力的依赖程度是不一样的.因此研究     

可逆与不可逆氢在甲烷化反应中的作用

用自行设计和建立的加压动态分析装置研究了甲烷化催化剂上氢的吸附和反应行为．结果表明，在反应条件下吸附的氢可区分为不可逆吸附氢和可逆吸附氢两类，不可逆吸附氢又可分为能被ＣＯ顶替出来的和不能被顶替的两种．起甲烷化反应的是可逆吸附氢，而能被ＣＯ顶替出来的不可逆氢对吸附ＣＯ起促进作用，不能被ＣＯ顶替出来的不可逆氢是甲烷化催化剂必不可少的组分（或称“促进剂”）．     

可逆与不可逆吸附的CO在甲烷化反应中的作用

在自行设计和建立的加压动态分析装置上,研究了工业甲烷化催化剂(Ni/Al_2O_3)上CO的吸附和反应行为。结果表明,在反应温度250℃下催化剂上吸附的CO有可逆吸附和不可逆吸附之分,甲烷的生成是与不可逆吸附的CO作用的结果,而可逆吸附CO则与生成乙烷、丙烷等密切相关。同时发现甲烷化反应过程的发生必须以不可逆吸附的氢存在为前提,且催化剂上不可逆吸附的氢可分为两部分,一部分可以被CO顶出,这部分氢可能起到了诱导CO吸附的作用;另一部分不可逆吸附的氢不能被CO顶出,这部分氢可能是构成催化剂不可缺少的“组分”(或称“促进剂”)。     

氢气存在下一氧化碳偶联反应的化学和性能

实验研究了在氢气存在下，一氧化碳与亚硝酸乙酯偶联合成草酸二乙酸反应体系在典型操作条件下的化学反应和反应性能，结果表明氢气只与反应体系中的亚硝酸乙酯反应生成乙醇。由于氢气与一氧化碳在催化剂表面竞争吸附，并且氢的存在打破了生成草酸二乙酯所必需的正常的氧化还原过程：Pd^0→Pd^2 →Pd^0，因此氢的引入使一氧化碳转化率及草酸二乙酯选择性下降。此外，化学吸附测试结果表明氢气和一氧化碳是在催化剂表面同一活性中心上吸附。     

Cuβ催化剂上氧化羰基合成碳酸二甲酯的原位漫反射红外光谱研究

采用原位漫反射红外光谱法研究了Cuβ催化剂上氧化羰基合成碳酸二甲酯(DMC)的反应机理,考察了甲醇、一氧化碳和DMC的单独吸附及混合气吸附。结果表明,Cuβ催化剂上只存在一种活性位,位于六元环中;氧气能够氧化吸附态的甲醇产生甲氧基和水;DMC吸附在Cuβ催化剂上时,以羰基中的氧原子吸附在活性位上更加稳定;反应存在生成单甲氧基物种和双甲氧基物种两条路径,单甲氧基物种与CO反应生成单甲基碳酸盐物种(MMC),MMC再与甲氧基反应生成DMC;CO插入双甲氧基物种也可以得到DMC。在Cuβ催化剂上更倾向于进行CO插入双甲氧基物种这一路径。     

超临界流体中CO和H2吸附过程的Monte Carlo模拟

利用Monte Carlo (MC) 方法,研究了一氧化碳和氢气在不同密度正己烷中的等温吸附情况.模型考虑了正己烷密度对一氧化碳和氢气在催化剂表面吸附量与吸附速率的影响.结果表明,主要有三个因素会影响溶质的吸附量:当溶剂密度低于其临界密度时,体系压力是影响溶质吸附量的主要因素；当体系处于超临界区时,超临界溶剂的溶解能力以及溶质和溶剂之间的竞争吸附是影响溶质吸附量的主要因素.在一定范围内增加溶剂的密度（压力）可以提高溶质在催化剂表面的吸附速率.     

UHV Studies of Methanol Decomposition on Mono‐ and Bimetallic CoPd Nanoparticles Supported on Thin Alumina Films

Bimetallic nanoparticles often turn out to be superior to the corresponding monometallic systems with respect to their catalytic properties. To study such effects for the methanol decomposition reaction, model catalysts were prepared by physical vapor deposition of Pd and Co under ultrahigh‐vacuum (UHV) conditions. Monometallic Pd and Co particles as well as CoPd core–shell particles were generated on an epitaxial alumina film grown on NiAl(110). The interaction with methanol is examined by temperature‐programmed desorption of methanol and carbon monoxide and by X‐ray photoelectron spectroscopy. The decomposition of methanol proceeds in two reaction pathways independent of the particle composition: complete dehydrogenation towards carbon monoxide and hydrogen, and C? O bond scission yielding carbon deposits. Pd is the most active material studied here. The relative importance of the two channels varies for the different particle systems: on Pd dehydrogenation is preferred, whereas the C? O bond cleavage is more pronounced on Co. The bimetallic clusters show a moderate performance for both pathways. Carbon deposition poisons the model catalysts by blocking the adsorption sites for methoxide, which is the first intermediate product during methanol decomposition. In particular on Co, large amounts of carbon deposits can also be caused by dissociation of the final product of the dehydrogenation pathway, carbon monoxide. A comparison with the results of methanol decomposition on Co, Pd, and CoPd catalysts in continuous‐flow reactors demonstrates that the findings of the present UHV study are relevant for catalytic performance under high‐pressure conditions.     

Investigation of the effect of carbon monoxide on the oxidative carbonylation of methanol to dimethyl carbonate over CuX and CuZSM-5 zeolites

Direct synthesis of dimethyl carbonate offers prospects for a “green chemistry” replacement to eliminate use of phosgene for polymer production and other processes. The carbonylation of methanol to produce dimethyl carbonate over Cu⁺X and Cu⁺ZSM-5 zeolites prepared by solid-state ion exchange has been investigated, focusing on the interaction of carbon monoxide with the Cu⁺ zeolites. The methanol carbonylation mechanism reported previously has been extended to account for carbon monoxide adsorption at high pressure. The comparison of the results obtained from Cu⁺X and Cu⁺ZSM-5 show that strong CO adsorption on the catalyst is not related to increased rate of dimethyl carbonate production. The rate limiting step for DMC production is best described as the Eley-Rideal reaction of gas-phase CO with surface methoxide.     

Scanning electrochemical microscopy of hydrogen electro-oxidation. Rate constant measurements and carbon monoxide poisoning on platinum

We describe an application of the scanning electrochemical microscope that uses tip–sample feedback to characterize the electro-oxidation of hydrogen on a polycrystalline platinum electrode in sulfuric acid solutions in the presence and absence of adsorbed carbon monoxide. The hydrogen oxidation reaction is probed by reducing protons at a diffusion-limited rate at the microscope's tip electrode while it is positioned near a platinum substrate. A series of approach curves measured as a function of the substrate potential provides hydrogen oxidation rate constant values over a wide range of substrate conditions. In the absence of CO, the rate of hydrogen oxidation exceeds 1 cm s⁻¹ at potentials within the hydrogen adsorption and double layer charging regions. A Tafel slope of 30 mV per decade is determined near the reversible potential. At increasingly positive substrate potentials, the hydrogen oxidation rate decreases exponentially with increasing potential as the surface is covered with an oxide layer. The adsorption of solution-phase carbon monoxide completely deactivates the platinum substrate towards steady-state hydrogen oxidation over a large range of substrate potentials. Approach curves indicate a near-zero rate constant for hydrogen oxidation on CO-covered platinum at potentials below oxide formation. An increase in the hydrogen oxidation rate is seen at potentials sufficiently positive that CO fails to adsorb and the platinum oxide forms. In comparison, dynamic tip–substrate voltammetry depicts a complex substrate response whereby the adsorbed carbon monoxide layer transforms from a weakly adsorbed state at low potentials to a strongly adsorbed state at high potentials. Although steady-state approach curve measurements depict the complete deactivation of catalytic activity at these potentials, a significant hydrogen oxidation current is observed during the potential-induced transformation between these weakly and strongly adsorbed CO states. The rate of hydrogen oxidation approaches that of a pristine platinum surface during this surface transformation before returning to the poisoned state.