乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni<sub>3</sub>Fe NPs@C双金属催化剂

引用本文: 王豪杰, 陈春, 张海民, 汪国忠, 赵惠军. 乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni₃Fe NPs@C双金属催化剂[J]. 催化学报, 2018, 39(10): 1599-1607. doi: 10.1016/S1872-2067(18)63105-5 shu

Citation: Haojie Wang, Chun Chen, Haimin Zhang, Guozhong Wang, Huijun Zhao. An efficient and reusable bimetallic Ni₃Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone[J]. Chinese Journal of Catalysis, 2018, 39(10): 1599-1607. doi: 10.1016/S1872-2067(18)63105-5 shu

乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni₃Fe NPs@C双金属催化剂

a 中国科学院固体物理研究所, 环境与能源纳米材料中心, 安徽合肥 230031, 中国;
b 中国科学技术大学, 安徽合肥 230026, 中国;
c 格里菲斯大学, 清洁环境与能源中心, 昆士兰4222, 澳大利亚
基金项目:
国家自然科学基金（51502297，51372248，51432009）；中国科学院科研装备研制项目（yz201421）.

摘要: 生物质经催化转化合成燃料及化学品是当前研究的热点.目前，生物质的催化转化主要聚焦于纤维素、半纤维素和木质素的解聚及其下游产物合成.其中，乙酰丙酸（LA）作为纤维素解聚的主要产物之一，是一种极具竞争力的平台化合物和重要的生物质转化中间体.LA通过催化转化可以合成各类高附加值的化学品，例如，通过催化加氢LA可选择性合成γ-戊内酯（GVL）.所合成的GVL用途广泛，可作为绿色溶剂、食品、燃料添加剂、（塑料、高分子、烃类或者其它高附加值化学品）前驱体等.目前，LA-to-GVL的研究主要着眼于非均相催化体系，包括负载型贵金属和非贵金属催化剂体.其中，贵金属催化剂主要有Ru，Au，Pd，Rh，Ir和Pt，虽然催化效率高，条件温和，但是成本高，难以实现工业化.此外对于广泛使用的Ru/C催化剂，存在金属-载体间相互作用不强.活性组分易流失、导致催化剂稳定性差等问题；而非贵金属则普遍存在催化活性不佳及反应条件苛刻等缺点.因此，开发高效、稳定、反应条件温和且具有工业化应用前景的非贵金属催化剂具有显著的研究意义，这也是当前的研究趋势.
在特定温度下，金属离子与碳基底存在较强的相互作用.鉴于此，本文通过一步碳热还原法合成了活性炭负载的Ni₃Fe双金属催化剂（Ni₃Fe NPs@C）.该催化剂在LA-to-GVL转化体系中展现了直接加氢（DH）和转移加氢（TH）双功能催化特性.首先，考察了其在DH体系中的反应特性：在130℃和2 MPa氢压反应条件下经2 h反应，LA转化率达到93.8%，GVL选择性为95.5%，GVL产率是相应的单金属Ni/C和Fe/C催化剂的6倍和40倍.此外，在TH催化反应体系中，在180℃，0.5 h和无外加氢源的反应条件下，以异丙醇为反应溶剂和供氢体，LA几乎完全转化为GVL，其反应效率同样相较于单金属Ni/C和Fe/C催化剂大幅度提高.所合成的Ni₃Fe NPs@C双金属催化剂DH和TH催化性能优于绝大多数报道的LA加氢贵金属和非贵金属催化剂.而且，该催化剂具有良好的循环利用性能，经过四次循环，其结构和化学状态没有发生明显的改变，稳定性明显优于商业化的Ru/C催化剂.此外，通过系统分析其催化性能以及材料结构，明确了该催化剂在LA的DH和TH反应体系中的活性位点，并提出了可能的反应路径.该研究为其它类型的DH和TH反应体系以及生物质高效转化过程提供了新的催化剂设计思路.并且这种催化剂及其制备方法简单、绿色，易于工业化推广和应用.

关键词:

English

An efficient and reusable bimetallic Ni₃Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

a Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, Anhui, China;
b University of Science and Technology of China, Hefei 230026, Anhui, China;
c Centre for Clean Environment and Energy, Griffith University, Queensland 4222, Australia
Received Date: 29 March 2018
Revised Date: 25 May 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (51502297, 51372248, 51432009), and the Instrument Developing Project of the Chinese Academy of Sciences (yz201421).

Abstract: Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity, selectivity and stability in catalytical conversion. Herein, we report a facile one-pot carbothermal route to in-situ controllable synthesize heterogeneous bimetallic Ni₃Fe NPs@C nanocatalyst. The X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-description results reveal that the Ni₃Fe alloy nanoparticles are evenly embedded in carbon matrix. The as-prepared Ni₃Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid (LA) to γ-valerolactone (GVL) via both direct hydrogenation (DH) and transfer hydrogenation (TH). In DH of LA, the bimetallic catalyst achieved a 93.8% LA conversion efficiency with a 95.5% GVL selectivity and 38.2 mmol g^-1 h^-1 GVL productivity (under 130℃, 2MPa H₂within 2 h), which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts, respectively. In addition, the identical catalyst displayed a full conversion of LA with almost 100% GVL selectivity and 167.1 mmol g^-1 h^-1 GVL productivity at 180℃ within 0.5 h in TH of LA. Under optimal reaction conditions, the DH and TH catalytic performance of 500-Ni₃Fe NPs@C(3:1) catalyst for converting LA to GVL is comparable to the state-of-the-art noble-based catalysts. The demonstrated capability of bimetallic catalyst design approach to introduce dual-catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni₃Fe NPs@C双金属催化剂

English

An efficient and reusable bimetallic Ni₃Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni3Fe NPs@C双金属催化剂

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An efficient and reusable bimetallic Ni3Fe NPs@C catalyst for selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

乙酰丙酸选择性加氢合成γ-戊内酯中高效和可循环使用的Ni₃Fe NPs@C双金属催化剂

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CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs