Research Article pubs.acs.org/acscatalysis
Activity and Selectivity in Nitroarene Hydrogenation over Au Nanoparticles on the Edge/Corner of Anatase Liang Wang,*,† Jian Zhang,† Hong Wang,*,‡ Yi Shao,§ Xiaohui Liu,§ Yan-Qin Wang,§ James P. Lewis,‡ and Feng-Shou Xiao*,†,∥ †
Key Lab of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, China Department of Physics and Astronomy, West Virginia University, Morgantown West Virginia 26506-6315, United States § Institute of Catalysis, East China University of Science and Technology, Shanghai 200237, China ∥ Key Lab of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, China ‡
S Supporting Information *
ABSTRACT: Highly selective hydrogenation of molecules containing more than one reducible group is always challenging. Here we report an efficient strategy for rational preparation of highly selective gold-based catalysts in the hydrogenation of substituted nitroarenes by positioning gold nanoparticles on the edge/corner sites of anatase. Mechanistic studies reveal that the catalyst with gold nanoparticles on the edge/ corner sites of anatase could form unique sites for selective adsorption and activation of nitro groups, thus leading to high activity and selectivity. This strategy for preparation of supported gold catalysts opens a new door for the design of highly efficient heterogeneous catalysts in the future. KEYWORDS: gold nanoparticle, nitrobenzene hydrogenation, high activity, anatase, adsorption, selectivity
1. INTRODUCTION The metal-catalyzed hydrogenations with molecular hydrogen have been regarded as a great discovery in the production of fine chemicals and pharmaceuticals.1−9 In these reactions, when more than one reducible group is present on substrate molecules, selective hydrogenation of the target group is challenging because the side reactions easily occur on the nontarget groups.10−20 One efficient approach for solution of this problem is to poison/block some of the atoms on the catalyst surface by additives such as quinoline, carbon monoxide, thiol ligands, and metal-based modifiers.21−25 Because numerous studies have demonstrated the differences in catalytic activity or selectivity when reactions occurs on different sites of the metal nanocrystals,26−28 poisoning/ blocking the sites for undesired reactions could achieve encouraging progress for improving catalytic selectivities.29,30 A prominent example is the industrial Lindlar catalyst. However, in most of these cases, catalytic activities are remarkably reduced due to poisoning the catalysts.21,22 In addition, leaching of these additives in the catalytic systems is difficult for the catalyst recycling. Therefore, it is strongly desirable to simultaneously enhance the catalytic activity and selectivity in the hydrogenation. Hydrogenation of substituted nitroarenes is chosen as a model in this work because these hydrogenated products are industrially important intermediates for the formation of fine chemicals and high-performance rubbers and polymers.2,31−38 Recently, it is reported that TiO2-supported Au nanocatalysts (Au/TiO2) are successful for selective hydrogenation of © 2016 American Chemical Society
substituted nitroarenes to anilines by selective adsorption of the nitro groups.2,38 This discovery leads to a series of investigations in this field, but the poor activities of Au/TiO2 catalysts still hinder the practical applications.2,31,35,36 An attractive strategy for enhancing catalytic activities of the Au/ TiO2 catalysts is to rationally design their structures, and successful examples are preparation of highly active catalysts for the water−gas shift and various oxidations,39−44 but it is still not successful for enhancement of catalytic activity in the nitroarene hydrogenation by adjusting the structure of the Au/ TiO2 catalysts. To understand the dependence of the Au/TiO2 structure on the activity in the nitroarene hydrogenation, a theoretical simulation for the adsorption of nitrobenzene molecule on the Au/TiO2 with different structures has been studied. Very interestingly, it is observed that the adsorption of the nitrobenzene on the edge/corner sites of TiO2 support is stronger than that on the (101) facet of TiO2 (see the details in Figure S1). On the basis of the well-known knowledge that the adsorption is a very important step in hydrogenation of nitroarenes,38 it is suggested that the Au nanoparticles loaded on the edge/corner sites of TiO2 support (Au/TiO2-EC) could improve the catalytic activities. As we expected, when the Au/ TiO2-EC is used to catalyze hydrogenation of 3-nitrostyrene, the turnover frequency of 279 h−1 is obtained. This value is Received: February 22, 2016 Revised: May 13, 2016 Published: May 19, 2016 4110
DOI: 10.1021/acscatal.6b00530 ACS Catal. 2016, 6, 4110−4116
Research Article
ACS Catalysis much higher than those ( 0, while the blue color density indicates that the Fukui Function at that site is negative f 0 (r) < 0; (B) CO-adsorption IR spectra of the Au/TiO2-EC and Au/TiO2-Con; (C) The zoomed-in image of the most energetic favorable structure of nitrobenzene attached on Au13/TiO2 model with one oxygen vacancy.
Table 1. Catalytic Data in the Hydrogenation of Different Molecules over Various Catalystsa substrate 3-nitrostyrene
2-chloro-4-nitrophenol 2-nitroacetophenone
catalyst
conditionsb
conv. (%)
sel.c (%)
Au/TiO2-EC Au/TiO2-Con Au/TiO2-Con Au/TiO2 Au−Pd/TiO2 Au/TiO2-EC Au/TiO2-Con Au/TiO2-EC Au/TiO2-Con
90 °C/10 bar/4.5 h 90 °C/10 bar/4.5 h 90 °C/10 bar/7 h 120 °C/9 bar/6 h 120 °C/9 bar/0.03 h 100 °C/10 bar/2 h 100 °C/10 bar/2 h 100 °C/10 bar/2 h 100 °C/10 bar/2 h
99.0 55.5 71.1 98.5 99.5 98.3 60.0 99.3 67.3
99.0 93.3 93.1 95.9d 0d 99.5 91.0 99.0 97.0
a
Reaction conditions: 0.8 mmol of nitrobenzene, 40 mg of catalyst, 3 mL of toluene. The molecular formula of substrates, and products are presented in Scheme S1. bReaction temperature/H2 pressure/reaction time. cSelectivity to the corresponding substituted aniline product. dThe data are from ref 2.
99.0−99.5%, which are much higher than those (91.0−97.0%, Table 1) over the Au/TiO 2-Con catalyst, indicating the excellent selectivity of Au/TiO2-EC catalyst. On the basis of these results, one can assume that the Au/TiO2-EC is more specific than Au/TiO2-Con to catalyze the reduction of nitro group due to the strong adsorption of nitro group on Au/TiO2EC, as confirmed by the IR study. To check this hypothesis, hydrogenation of various groups were carried out separately by employing them as substrates. As summarized in Table 2, both Au/TiO2-EC and Au/TiO2-Con are active for the hydrogenation of all substrates. When nitrobenzene, styrene, acetophenone, and chlorobenzene were physically mixed as substrate, the Au/TiO2-EC is only active for hydrogenation of the nitrobenzene, where the hydrogenation of other groups (e.g., −Cl, −CO, CC) are prevented in the complete hydrogenation reactions. In comparison, the Au/TiO2-Con is still active for hydrogenation of the nitrobenzene, styrene, and acetophenone (Table 2). These results indicate the obvious advantage of the Au/TiO2-EC in selective hydrogenations, compared with the Au/TiO2-Con.
lead to the high catalytic activity in hydrogenation of nitrobenzene. 3.4. Hydrogenation Selectivity. The hydrogenation of 3nitrostyrene was performed to study the catalytic selectivity, because the vinyl groups are very active in the hydrogenation. Although Au nano catalysts have been reported to exhibit more than 90% selectivity in the hydrogenation of 3-nitrostyrene to 3-aminostyrene,2 it is surprising to observe that the selectivity could be further improved over the Au/TiO2-EC, giving the 3aminostyrene selectivity at 99.0%, as shown in Table 1. Under the same reaction conditions, the Au/TiO2-Con gives really lower conversion and selectivity at 55.5 and 93.3%, respectively. This phenomenon is reasonably attributed to selectively and strongly adsorbing the nitro group of 3-nitrostyrene molecule on Au/TiO2-EC (Figures S8−S11). In addition, the chemoselective reduction of nitro group in the presence of carbonyl, phenol, and chlorine groups has been studied through the hydrogenation of 2-chloro-4-nitrophenol and 2-nitroacetophenone (Scheme S1). In these cases, the Au/TiO2-EC always exhibits excellent selectivity to the corresponding amines at 4114
DOI: 10.1021/acscatal.6b00530 ACS Catal. 2016, 6, 4110−4116
Research Article
ACS Catalysis
TiO2−EC still gives the conversion at 96.7% and 3-aminostyrene selectivity at 99.0% (Scheme S2). In this case, the turnover frequency (TOF) of the Au/TiO2-EC could reach to 279 h−1 calculated from the total amount of Au in the reaction system. This TOF value (279 h−1), which is obtained even under relatively mild reaction conditions, is still much higher than that (
