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The crucial role of catalysts in the reaction of low temperature decomposition of hydrogen sulfide: Non-equilibrium thermodynamics of the irreversible process in an open system
Molecular Catalysis ( IF 4.6 ) Pub Date : 2020-10-12 , DOI: 10.1016/j.mcat.2020.111240
A.N. Startsev

The reaction mechanisms of low-temperature H2S decomposition on sulfide and metal catalysts are considered in the framework of thermodynamics of non-equilibrium irreversible biological processes for open systems, since these reactions occur at room temperature without supplying thermal energy from the outside owing to the internal energy of substrate molecules – hydrogen sulfide. On sulfide catalysts the irreversible process of H2S decomposition proceeds through the stage of formation of hydrogen disulfide (disulfane), H2S2, as a key intermediate, and the reaction products are hydrogen and solid sulfur. The reaction occurs through a sequence of consecutive exothermic stages of dissociation of H2S molecules, in which the entropy of the system is reduced due to its dissipation into environment as the bound (waste) energy TΔS. The remaining part of the free energy ΔG is accumulated on the catalyst surface and is used for the implementation of the energy-intensive step of decomposition of the adsorbed intermediate. Similarly, the metal catalyst provides capture and accumulation of energy from the exothermic processes of adsorption and dissociation of the initial H2S molecules in the atomic adsorbed species of hydrogen and sulfur. The stored energy is used for chemical conversion of adsorbed intermediates into the final reaction products – molecular hydrogen and diatomic triplet sulfur, followed by it does desorption into the gas phase. When H2S is decomposed on metal catalysts at room temperature, along with hydrogen, previously unknown diatomic gaseous sulfur in the ground triplet state is obtained, the existence of which is predicted by quantum chemistry. Some properties of the triplet sulfur and the white globular hexagonal sulfur obtained from its saturated aqueous solutions (which is also a previously unknown allotrope of solid sulfur) are considered. Similarity of the morphology of hydrophilic white sulfur globules and bacterial colorless sulfur S0 obtained by sulfur bacteria in the processes of chemosynthesis of organic matter from CO2 and H2S, allowed to develop an alternative hypothesis about the nature of bacterial sulfur S0 and possible mechanism of chemosynthesis of carbohydrates with the participation of sulfur bacteria. Apparently, the low-temperature catalytic decomposition of hydrogen sulfide is the first example in heterogeneous catalysis, when the principles of non-equilibrium biological thermodynamics in open systems are used to justify the possibility implementing a heterogeneous catalytic reaction.



中文翻译:

催化剂在硫化氢的低温分解反应中的关键作用:开放系统中不可逆过程的非平衡热力学

在开放系统的非平衡不可逆生物过程的热力学框架中考虑了硫化物和金属催化剂上低温H 2 S分解的反应机理,因为这些反应在室温下发生,而由于以下原因不会从外部提供热能底物分子的内部能量–硫化氢。在硫化物催化剂上,H 2 S分解的不可逆过程通过形成二硫化氢(二硫),H 2 S 2作为关键中间体的阶段进行,反应产物为氢和固体硫。该反应通过H 2分解的一系列连续放热阶段发生小号分子,其中,所述系统的熵由于减少到它耗散到环境为结合的(废料)能量TΔ小号。自由能量ΔG的剩余部分积聚在催化剂表面上,并用于执行吸附的中间体分解的能量密集型步骤。类似地,金属催化剂从氢和硫的原子吸附物种中初始H 2 S分子的吸附和解离的放热过程中捕获和积累能量。存储的能量用于将吸附的中间体化学转化为最终反应产物-分子氢和双原子三重态硫,然后解吸为气相。当H2 S在室温下在金属催化剂上与氢一起分解,获得了以前未知的基态三重态双原子气态硫,其存在是通过量子化学预测的。考虑了三重态硫和从其饱和水溶液中获得的白色球形六边形硫的一些性质(这也是固体硫的同素异形体)。在从CO 2和H 2 S化学合成有机物的过程中,由硫细菌获得的亲水性白硫小球和细菌无色硫S 0的形态相似,可以为细菌硫S 0的性质提出另一种假设。硫细菌参与的化学合成碳水化合物的可能机制。显然,硫化氢的低温催化分解是非均相催化的第一个例子,当使用开放系统中的非平衡生物热力学原理来证明实施非均相催化反应的可能性时,就可以了。

更新日期:2020-10-12
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