Theoretical insights into the promotion effect of subsurface boron for the selective hydrogenation of CO to methanol over Pd catalysts

doi:10.1039/c6cp02735k

	Theoretical insights into the promotion effect of subsurface boron for the selective hydrogenation of CO to methanol over Pd catalysts
	Wu, Panpan; Yang, Bo
	2016-08-31
发表期刊	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN	1463-9076
卷号	18 期号:31 页码:21720-21729
发表状态	已发表
DOI	10.1039/c6cp02735k
摘要	The activity and selectivity of methanol synthesis from syngas have been studied for decades from both experimental and theoretical aspects. In this work, CO hydrogenation to methanol on both Pd(211) and subsurface boron-modified Pd(211) surfaces is investigated based on density functional theory calculations. Methane formation is considered as the main competitive reaction in the process and all the barriers and reaction energies involved are also calculated. We find that the modification of boron atoms will not alter the corresponding favored reaction pathways to produce methanol and methane on Pd(211), namely CO -> CHO -> CHOH -> CH2OH -> CH3OH for methanol formation and CO -> COH -> C -> CH -> CH2 -> CH3 -> CH4 for methane formation. In addition, by using a two-step model to estimate the effective barriers for methanol and methane formation, the activity and selectivity for the product formation could be obtained and compared. It is found that the addition of boron atoms would significantly increase the activity of methanol formation while the activity of methane formation on clean and boron modified Pd surfaces is similar. Furthermore, we find that the hydrogenation of CO over clean Pd(211) will give high methane selectivity, whilst the boron modified Pd(211) mainly produces methanol. All these observed results can be explained by the electronic interaction between boron atoms and local Pd atoms through the lattice strain effect and alloying effect, resulting in the downshift of the d-band center of surface Pd away from the Fermi level. Finally, an extended Bronsted-Evans-Polanyi (BEP) relationship is found between the energies of the transition states and the initial/final states for hydrogenation/dissociation reactions, which may provide significant insight into the activity and selectivity of the catalysts for methanol synthesis.
收录类别	SCI
语种	英语
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:000381418000081
出版者	ROYAL SOC CHEMISTRY
WOS关键词	DENSITY-FUNCTIONAL THEORY ; UNSUPPORTED COPPER-CATALYSTS ; TOTAL-ENERGY CALCULATIONS ; AUGMENTED-WAVE METHOD ; PALLADIUM CATALYSTS ; HETEROGENEOUS CATALYSIS ; CARBON-MONOXIDE ; METAL-SURFACES ; SYNTHESIS GAS ; ACETYLENE HYDROGENATION
原始文献类型	Article
引用统计
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/1744
专题	物质科学与技术学院物质科学与技术学院_PI研究组_杨波组物质科学与技术学院_博士生
通讯作者	Yang, Bo
作者单位	ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院
第一作者的第一单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Wu, Panpan,Yang, Bo. Theoretical insights into the promotion effect of subsurface boron for the selective hydrogenation of CO to methanol over Pd catalysts[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2016,18(31):21720-21729.
APA	Wu, Panpan,&Yang, Bo.(2016).Theoretical insights into the promotion effect of subsurface boron for the selective hydrogenation of CO to methanol over Pd catalysts.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,18(31),21720-21729.
MLA	Wu, Panpan,et al."Theoretical insights into the promotion effect of subsurface boron for the selective hydrogenation of CO to methanol over Pd catalysts".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 18.31(2016):21720-21729.