Abstract：
BACKGROUND: The hydrogen cyanide (HCN) hydrolysis reaction mechanism over Al-doped graphene was investigated through the density functional theory method. HCN preferentially adsorbed vertically on the Al top site to form a stable adsorption configuration. H2O preferentially adsorbed parallel on the Al top site to form a stable adsorption configuration. The competitive adsorption of HCN and H2O weakened the adsorption stability of each molecule over Al-doped graphene. The break of C-N and H-O bonds was the key process in the preferential fracture pathway of the C-H bond. The break of C-N and C-H bonds was the key process in the preferential fracture pathway of the H-O bond. HCN played the role of bridge in the joint adsorption process. H atom transfer and C-N bond cleavage promoted the generation of CO and NH3. The change in the order of H atom transfer determined the reaction energy barrier. NH2CHO was more likely to act as an intermediate to promote the hydrolysis process.
METHODS: The calculation work was achieved from the Dmol3 program in Material Studio 2017 using the GGA/PBE method with DNP basis, including the geometric structure and reaction pathway optimization, and adsorption energy calculation. All calculations were performed using a spin-polarized set and the TS method was used for DFT-D correction.
METHODS: The calculation work was achieved from the Dmol3 program in Material Studio 2017 using the GGA/PBE method with DNP basis, including the geometric structure and reaction pathway optimization, and adsorption energy calculation. All calculations were performed using a spin-polarized set and the TS method was used for DFT-D correction.
摘要：
背景：通过密度泛函理论方法研究了氰化氢（HCN）在Al掺杂石墨烯上的水解反应机理。HCN优先垂直吸附在Al顶部位点上，形成稳定的吸附构型。H2O优先平行吸附在Al顶位上，形成稳定的吸附构型。HCN和H2O的竞争吸附削弱了各分子在Al掺杂石墨烯上的吸附稳定性。C-N和H-O键的断裂是C-H键优先断裂途径中的关键过程。C-N和C-H键的断裂是H-O键优先断裂途径中的关键过程。HCN在联合吸附过程中起到了桥梁的作用。H原子转移和C-N键断裂促进了CO和NH3的生成。H原子转移顺序的变化决定了反应能垒。NH2CHO更可能充当促进水解过程的中间体。
方法：计算工作是从MaterialStudio2017中的Dmol3程序中使用具有DNP基础的GGA/PBE方法实现的，包括几何结构和反应途径的优化，和吸附能量计算。使用自旋极化集进行所有计算,并将TS方法用于DFT-D校正。
方法：计算工作是从MaterialStudio2017中的Dmol3程序中使用具有DNP基础的GGA/PBE方法实现的，包括几何结构和反应途径的优化，和吸附能量计算。使用自旋极化集进行所有计算,并将TS方法用于DFT-D校正。
