氧原子在θ-Fe_(3)C不同晶面的吸附及移除机理  

Adsorption and removal mechanism of atomic oxygen on different facets ofθ-Fe_(3)C

作　　者：白亚 郑昱 李永峰 刘金家 BAI Ya;ZHENG Yu;LI Yongfeng;LIU Jinjia(Department of Energy Chemistry and Materials Engineering,Shanxi Institute of Energy,Jinzhong 030600,China;National Energy Center for Coal to Clean Fuels,Synfuels China Company Ltd,Beijing 101400,China)

机构地区：[1]山西能源学院能源化学与材料工程系,山西晋中030600 [2]中科合成油技术股份有限公司,北京101400

出　　处：《燃料化学学报（中英文）》2024年第10期1435-1442,共8页Journal of Fuel Chemistry and Technology

基　　金：山西省自然科学基金(202303021212294)资助。

摘　　要：碳化铁θ-Fe_(3)C作为费托反应活性相之一,其氧化造成了催化剂的严重失活。探究氧原子在碳化铁晶面的吸附及移除机理有助于理解氧化过程,为提高催化剂的稳定性提供参考。本工作通过理论计算研究了低覆盖度下氧原子在θ-Fe_(3)C不同晶面的吸附,其在(110)晶面吸附最强,(001)晶面次之,(011)晶面吸附最弱,即(110)容易氧化。原子热力学研究表明,增大H_(2)O分压或降低温度有利于氧原子吸附,容易造成表面氧化。此外,在典型费托反应条件下(110)晶面氧原子的覆盖度最高,进一步证明该晶面易氧化,与低覆盖度吸附结果一致。对移除路径进行计算得出,(011)晶面吸附氧原子直接与CO反应以CO_(2)方式移除能垒较低(0.84 eV);(001)与(110)晶面吸附氧原子主要通过OH歧化以H_(2)O方式移除,但后者形成O−H键需要克服的能垒更高(1.72 vs 1.47 eV)。The Fisher-Tropsch Synthesis(FTS)is one of the most intensively studied reactions in heterogeneous catalysis,which could convert the syngas(CO and H_(2))from coal,natural gas,shale gas,and biomass into gasoline,diesel,and a series of important chemical products.The process provides an effective strategy for reducing environmental pollution caused by direct coal combustion,at the meanwhile,alleviating dependence on imported petroleum.During the reaction,iron-based catalysts have attracted the attention of numerous researchers due to their unique advantages,for example,low cost,flexibility in product distribution,suitability for low H_(2)/CO ratio syngas and large operating space.And the iron-based catalysts in FTS have achieved applications successfully in industry.Iron carbide is recognized as active phases in FTS catalyzed by iron-based catalysts,among whichθ-Fe_(3)C is one of the dominant phases.Additionally,θ-Fe_(3)C is widely applied in fields such as biomedicine and electrochemistry.However,θ-Fe_(3)C could be oxidized under realistic conditions,affecting the performance as magnetic materials and catalysts seriously.Considering the case above,the investigation of oxidation of iron carbideθ-Fe_(3)C is of great significance.And exploring the adsorption,as well as removal mechanism of atomic oxygen over the iron carbide facet is helpful for understanding the oxidation process,and providing a reference for improving the stability of catalysts.In this work,we have explored the adsorption of oxygen atoms from low to high coverage on threeθ-Fe_(3)C surfaces with density functional theory.Ab initio atomistic thermodynamics was utilized to investigate the effect of experimental conditions like temperature and partial pressure of H_(2)O.According to the calculation,it was found that the adsorption at low coverage on(110)was the strongest,followed by(001),and the adsorption on(011)was the weakest,meaning that(110)can be oxidized easily.As the number of oxygen atoms adsorbed on the surface increases,the stepwise ads

关 键 词：θ-Fe_(3)C 氧化 氧原子吸附 移除机理 

分 类 号：O643[理学—物理化学]