Interstitial Carbon in Ni Enables High-Efficiency Hydrogenation of 1,3-Butadiene

doi:10.3866/PKU.WHXB202301012

IMR OpenIR

	Interstitial Carbon in Ni Enables High-Efficiency Hydrogenation of 1,3-Butadiene
	Dong, Shaoming 1,2; Pu, Yinghui 1,2; Niu, Yiming 1,2; Zhang, Lei 1; Wang, Yongzhao 1,2; Zhang, Bingsen 1,2
通讯作者	Niu, Yiming(ymniu14b@imr.ac.cn) ; Zhang, Bingsen(bszhang@imr.ac.cn)
	2023-11-15
发表期刊	ACTA PHYSICO-CHIMICA SINICA
ISSN	1000-6818
卷号	39 期号:10 页码:7
摘要	Selective hydrogenation is an essential catalytic reaction in modern industrial chemistry. For instance, butene can be used to produce many important organic chemical products, but the catalytic cracking of naphtha to produce olefins also produces some diolefins, which contain approximately 0.2%-2.0% 1,3-butadiene. The selective hydrogenation of 1,3-butadiene is a crucial step in purifying single olefins and prevents poisoning of the catalysts used in polymerization. Currently, the most common industrially employed catalysts in the reaction are palladium-based catalysts, but drawbacks associated with these include high cost and low abundance. Transition metal Ni-based catalysts have the advantages of being low cost and having high hydrogenation activity, but they are prone to excessive hydrogenation in butadiene hydrogenation reactions. This leads to reduced selectivity and the loss of monoolefins in the feed gas. In addition, Ni-based catalysts tend to accumulate carbon on the surface, which results in catalyst deactivation. Therefore, designing Ni-based catalysts with excellent catalytic performance has been an industrial research priority. Herein, we synthesized Ni3Zn/Al2O3 catalysts by impregnation and achieved the alumina-supported Ni3ZnC0.7 structure by acetylene atmosphere treatment. Interstitial sites of the Ni3Zn intermetallic catalyst were modified by introducing interstitial carbon atoms. This enhances the catalytic performance of the 1,3-butadiene hydrogenation reaction. X-ray diffraction and transmission electron microscopy revealed that the catalyst presents a typical Ni3ZnC0.7 phase. The interstitial carbon structure can suppress excessive hydrogenation, exhibiting up to 93% butene selectivity at a 98% conversion of 1,3 butadiene, which renders it superior to the Ni3Zn/Al2O3 catalyst. More importantly, the selectivity to 1-butene is improved by approximately 40% compared to the Ni3Zn/Al2O3 intermetallic catalyst. In addition, the Ni3ZnC0.7/Al2O3 catalyst exhibits superior and stable selectivity within a wide H2/1,3-butadiene ratio range and can operate reliably under fluctuating conditions. CO-DRIFTS demonstrated that coordinating the carbon atom in the interstitial site with the neighboring Ni atoms alters the electron structure of the Ni sites in the Ni3ZnC0.7 structure. The electrons at the surface Ni sites are transferred to the carbon atoms at the interstitial sites rendering Ni more electron-deficient and decreasing the adsorption strength of 1-butene, which inhibits the excessive hydrogenation reaction pathway. It is also noteworthy that the interstitial carbon structure can inhibit carbonaceous species formation and accumulation significantly improving the Ni3ZnC0.7/Al2O3 catalyst's stability. This work is significant for understanding the structure-performance relationship at the interstitial sites in transition metal catalysts. Furthermore, it provides new insights into the design of hydrogenation catalysts.
关键词	Ni-based catalyst Interstitial site Ni3ZnC0.7 Selective hydrogenation Subsurface carbon
资助者	National Natural Science Foundation of China ; Research Fund of Shenyang National Laboratory for Materials Science, China
DOI	10.3866/PKU.WHXB202301012
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[22072164] ; National Natural Science Foundation of China[22002173] ; National Natural Science Foundation of China[52161145403] ; Research Fund of Shenyang National Laboratory for Materials Science, China
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:001076778600005
出版者	PEKING UNIV PRESS
引用统计	被引频次：5[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/179311
专题	中国科学院金属研究所
通讯作者	Niu, Yiming; Zhang, Bingsen
作者单位	1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China 2.Univ Sci & Technol China, Sch Mat Sci & Engn, Shenyang 110016, Peoples R China
推荐引用方式 GB/T 7714	Dong, Shaoming,Pu, Yinghui,Niu, Yiming,et al. Interstitial Carbon in Ni Enables High-Efficiency Hydrogenation of 1,3-Butadiene[J]. ACTA PHYSICO-CHIMICA SINICA,2023,39(10):7.
APA	Dong, Shaoming,Pu, Yinghui,Niu, Yiming,Zhang, Lei,Wang, Yongzhao,&Zhang, Bingsen.(2023).Interstitial Carbon in Ni Enables High-Efficiency Hydrogenation of 1,3-Butadiene.ACTA PHYSICO-CHIMICA SINICA,39(10),7.
MLA	Dong, Shaoming,et al."Interstitial Carbon in Ni Enables High-Efficiency Hydrogenation of 1,3-Butadiene".ACTA PHYSICO-CHIMICA SINICA 39.10(2023):7.