Gao Yuzeng, Liu Fang Feixue, Wang Haolan, Xu Kainan, Chen Rongxin, Zhang Wenxin, Shi Yun
School of Chemistry & Chemical Engineering, Linyi University, Linyi, 276000, China.
J Mol Model. 2025 Jan 6;31(1):34. doi: 10.1007/s00894-024-06267-7.
In this work, a comparative study on the catalytic conversion of 5-hydroxymethyl furfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) on precious Pd(111) and nonprecious Cu(111) was systematically performed. On the basis of the calculated activation energy (E) and reaction energy (E), the optimal energy path for the hydrogenation of HMF (F-CHO) into BHMF (F-CHOH) on Pd(111) is as follows: F-CHO + 2H → F-CHOH + H → F-CHOH; the minimum reaction path on Cu(111) is F-CHO + 2H → F-CHO + H → F-CHOH. On Cu(111), the formation of F-CHOH from F-CHO hydrogenation is the rate-determining step because it has the highest reaction energy barrier and the smallest rate constant. The comparison of HMF hydrogenation on Pd(111) and Cu(111) reveals their inherent differences in selectivity, mainly due to the different adsorption configurations of HMF and BHMF, and it was concluded that the nonprecious Cu(111) is a promising hydrogenation catalyst for the production of BHMF from the hydrogenation of HMF.
All plane-wave DFT calculations were performed via the Vienna ab initio simulation package (VASP). The exchange and correlation energies were computed via the generalized gradient approximation (GGA) of the Perdew, Burke, and Ernzerhof (PBE) functional with the projector augmented wave (PAW) method.
在本研究中，系统地开展了在贵金属Pd(111)和非贵金属Cu(111)上5-羟甲基糠醛（HMF）催化转化为2,5-双（羟甲基）呋喃（BHMF）的对比研究。基于计算得到的活化能（E）和反应能（E），HMF（F-CHO）在Pd(111)上氢化生成BHMF（F-CHOH）的最优能量路径如下：F-CHO + 2H → F-CHOH + H → F-CHOH；在Cu(111)上的最小反应路径为F-CHO + 2H → F-CHO + H → F-CHOH。在Cu(111)上，F-CHO氢化生成F-CHOH是速率决定步骤，因为它具有最高的反应能垒和最小的速率常数。对Pd(111)和Cu(111)上HMF氢化反应的比较揭示了它们在选择性上的内在差异，这主要归因于HMF和BHMF不同的吸附构型，并且得出结论，非贵金属Cu(111)是一种由HMF氢化生产BHMF的很有前景的氢化催化剂。
所有平面波密度泛函理论（DFT）计算均通过维也纳从头算模拟软件包（VASP）进行。交换和关联能通过Perdew、Burke和Ernzerhof（PBE）泛函的广义梯度近似（GGA）结合投影增强波（PAW）方法进行计算。
