Selective Hydrogenation of Phenol: Chemnanomat February 2018

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Selective Hydrogenation of Phenol
Article in ChemNanoMat · February 2018

DOI: 10.1002/cnma.201800031
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DOI: 10.1002/cnma.201800031 Focus Review
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3 Selective Hydrogenation
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6 Selective Hydrogenation of Phenol
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Xiangqian Kong,[a] Yutong Gong,*[a] Shanjun Mao,[a] and Yong Wang*[a]
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ChemNanoMat 2018, 4, 1 – 20 1 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
These are not the final page numbers! ÞÞ
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1
2 Abstract: The selective hydrogenation of phenol to cyclo- the technology for catalyst design has developed rapidly
3 hexanone has attracted a great deal of attention both in within the past decades, direct evidence to understand the
4 industry and academia. In this review, the significance, reaction mechanisms and kinetics is still scarce. Therefore, it is
5 strategies and mechanisms for the production of cyclo- still challengingto explore the function mechanisms and
6 hexanone are briefly described. Then, the evolution of phenol design advanced catalysts with high activity and high
7 hydrogenation in gas/liquid phase is summarized according selectivity (> 95%) for direct hydrogenation of phenol to
8 to catalyst type. In situ hydrogenation techniques including cyclohexanone. This review may provide guidance for these
9 catalytic transfer hydrogenation (CTH) and electrocatalytic attempts.
10 hydrogenation (ECH) of phenol are also discussed. Although
11
12
13
14 1. Introduction catalyst followed by dehydrogenation to cyclohexanone on Cu/
15 Zn catalyts.[1,5–6] The ‘‘one-step’’ hydrogenation, or called
16 Cyclohexanone, an important industrial raw material, is widely selective hydrogenation, of phenol to cyclohexanone, shows its
17 used in the production of caprolactam and adipic acid, which superiority in numerous aspects. For instance, the tedious
18 are the key ingredients for the synthesis of nylon 6 and nylon product separation steps can be avoided and costs would be
19 66, respectively.[1] saved in the absence of the endothermic dehydrogenation
20 Industrial production of cyclohexanone is mainly realized by step.[1,7] With the development of highly performed catalysts,
21 two reaction routes, i. e., cyclohexane oxidation[2] (Figure 1, wider applications of selective hydrogenation of phenol to
22 cyclohexanone in industry can be expected in the near future.
23 Additionally, phenol is a well-known model compound of bio-
24 oil and its direct hydrogenation and hydrolysis are of great
25 significance for the sustainable chemistry.[8]
26 According to reaction conditions, the hydrogenation of
27 phenol can be divided into two types, say, gas-phase hydro-
28 genation and liquid-phase hydrogenation. Phenol hydrogena-
29 tion undergoes several reaction routes as follows (Figure 2): the
30
31
32
33
34
35
36
37
38
39 Figure 1. The industrial production routes of cyclohexanone.
40
41
42 blue) and phenol hydrogenation[3] (Figure 1, red and green).
43 Although the oxidation route is generally performed in industry
44 due to its relatively low cost, it suffers from drawbacks
45 including harsh reaction conditions (high temperature, high
46 pressure) and the generation of undesirable byproducts, which
47 lower the product yield and complicate the recovery/separation
48 steps.[4] Via hydrogenation techniques, phenol can be hydro-
49 genated to cyclohexanone in a ‘‘one-step’’ (Figure 1, red) or a
50 ‘‘two-step’’ manner (Figure 1, green).[5] The ‘‘two-step’’ process
51 involves hydrogenation of phenol to cyclohexanol over a Ni Figure 2. The reaction pathways of phenol hydrogenation.
52
53
54 [a] X. Kong, Dr. Y. Gong, Dr. S. Mao, Prof. Dr. Y. Wang partial hydrogenation of benzene ring of phenol, leading to the
55 Advanced Materials and Catalysis Group, Institute of Catalysis, Zhejiang intermediate of cyclohexenol, which is unstable and gives rise
University, Hangzhou 310028, P. R. China
56 E-mail: chemgyt@gmail.com to a rapid isomerization to cyclohexanone.[9] Cyclohexanone
57 chemwy@zju.edu.cn can be further hydrogenated to cyclohexanol, and cyclohexanol
ChemNanoMat 2018, 4, 1 – 20 www.chemnanomat.org 2 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1 can be hydrogenated from enol intermediate or from phenol many acidic sites to hydrogenate phenol. According to the
2 directly as well.[10] However, some studies also show that the “two-site” model proposed by Neri, a significant amount of
3 generation of cyclohexanone and cyclohexanol are two cyclohexanol should be produced if phenol adsorbed on the
4 independent processes.[11] At high reaction temperatures, acid sites of CHT in a co-planar form. But in fact, only 3–5% of
5 especially in gas-phase hydrogenation, excessive side reactions cyclohexanol generated among all the products. Therefore,
6 may occur such as hydrogenolysis of phenol to benzene, and Chen et al. raised a “one-site” model for the adsorption manner
7 dehydration of cyclohexanol to cyclohexene with further hydro-
8 genation to cyclohexane.[3a,9a] Forming these by-products
9 greatly reduces the yield of cyclohexanone, complicates
10 product separation and increases production costs. Thus, it is Xiangqian Kong studied in Northeast
11 still challenging to develop highly active and highly selective (> Forestry University and received her
12 95%) catalysts for hydrogenation of phenol to cyclohexanone. B.Eng. in 2016. She is currently a master
13 In this review, we mainly focus on the advancement of candidate at the Department of
Chemistry, Zhejiang University, under
14 direct hydrogenation of phenol to cyclohexanone in gas/liquid
the supervision of Prof. Yong Wang. Her
15 phase in the viewpoint of catalyst evolutions (Table 1 and 2). In research interests concern the design of
16 fact, although numerous exciting experimental studies have advanced catalysts and DFT theoretical
17 been carried out for this reaction, there are few scientific calculation in the selective hydrogena-
18 evidences concerning the detailed reaction mechanism with tion of phenol to cyclohexanone in gas
19 the assistance of surface-science techniques and kinetic analy- and liquid phase.
20 sis. Industrial production of cyclohexanone via phenol hydro-
21 genation might not be realized successfully unless we have a Yutong Gong received his BSc in
22 better understanding about the reaction mechanism of these Chemistry from Qufu normal University
23 catalysts with excellent performance. This summary here may in 2010. Afterwards, he finished his PhD
studies in Department of Chemistry of
24 trigger new design of highly performed catalysts and pursuit
Zhejiang University under the super-
25 for better understanding of the reaction mechanisms during vision of Haoran Li and Yong Wang. He
26 phenol hydrogenation. started his postdoctoral research in
27 Tokyo Institute of Technology with
28 Hideo Hosono in 2016 and rejoined the
29 2. Reaction Mechanism group of Yong Wang in Zhejiang
University from July, 2017. His current
30
research interests concern the heteroge-
31 It has been established that the adsorption pattern of reactants neous catalysis and energy conversion
32 plays an important role in phenol hydrogenation. Advancement materials.
33 in the understanding of the adsorption mode of reactants is a
Shanjun Mao studied in Shandong
34 step-by-step process, accompanied with a gradual revision and University from 2007 to 2011. He
35 unification. A brief introduction of such a development process received his Bachelor’s degree in 2014
36 is shown as follows. In 1972, Taylor et al. observed that the from Institute of metal Research, Chi-
37 overtone bands in the infrared spectrum (region 2000– nese Academy of Sciences. He is now a
38 1650 cm 1) related to the C H ring vibrations disappeared Ph.D. candidate under the supervision
of Prof. Yong Wang in Zhejiang Univer-
39 when phenol adsorbed on Al2O3. Based on the viewpoint that
sity. He now mainly focuses on the
40 the out-of-plane C H ring vibrations may be hindered when theoretical research on the catalytic
41 phenol adsorbed parallel to the surface of support, Taylor and mechanism and rational catalyst de-
42 coworkers suggested that the phenol molecule anchored on sign based on density functional theory.
43 the surface was oriented “co-planar” with the surface of Al2O3
44 owing to an interaction between the aromatic ring of phenol Prof. Dr. Yong Wang studied chemical
45 and the acid sites of Al2O3.[12] Tanabe et al. raised the same engineering at Xiangtan University
46 manner of phenol orientation on acidic silica-alumina but a from 1998 to 2002. He received his
47 “non-planar” form on basic MgO.[1] Based on the above work, Ph.D. degree from Zhejiang University
48 Neri et al. further put forward the theory of “two-site” in 2007. After a postdoctoral stay at the
Department of Chemistry, Zhejiang Uni-
49 adsorption in 1994, as shown in the Scheme 1c ~ d.[3a] Scirè et al.
versity, he joined the Max Planck
50 negated this point of view because they found that the Institute for Colloids and Interfaces in
51 overtone bands associated with the C H ring vibrations Potsdam/Germany in 2009. He rejoined
52 disappeared regardless of whether the phenol was adsorbed Zhejiang University and became a
53 on Al2O3 or MgO.[13] But the results in Scirè’s work showed that Professor for Chemistry in 2011. His
54 the addition of Pd did not change the spectrum of phenol research focuses on nanomaterials and
their applications in heterogeneous
55 adsorbed on Al2O3, which also indicated that phenol was
catalysis and energy storage and con-
56 adsorbed mainly on support.[13] In 1999, Chen and coworkers version.
57 prepared Pd/CHT (calcined Mg/Al hydrotalcite) catalyst with
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1 Table 1. Summary of catalysts for phenol hydrogenation in gas phase.
2
Catalysts T(oC) H2/phenol Experimental Reactor Phenol Cyclohexanone
3 Molar Ratio Parameters Conv. (%) Sel. (%)
4
1%Pt/silica gel[15] 150 19 (initial) W/F 0.48 kg h mol 1 Fixed bed reactor 66.0 51.0
5 1%Pt/silica gel[15] 150 19 (initial) W/F 0.85 kg h mol 1 Fixed bed reactor 96.0 78.0
6 5%Pt/C[7a] 200 4.7 H2 uptake 81.7 umol g 1cat Fixed bed reactor 64.5 83.9
7 5%Pt-0.5%Cr/C[7a] 200 4.7 H2 uptake 26.7 umol g 1cat Fixed bed reactor 55.0 100
5%Pt-0.5%Zr/C[28] 200 4.7 H2 uptake 20.1 umol g 1cat Fixed bed reactor 45.0 74.0
8 0.66%Pd-0.93%Ca/Al2O3[34] 160 10 TON 7 104 mol s 1 g 1Pd Glass tubular reactor 59.0* 89.0*
9 Pd Na/Al2O3[24] 230 5.4 WHSV 7.5 10 6 mol s 1 g 1cat Vertical flow reactor 88.0 > 95
10 1%Pd/UHT[19a] 180 4.0 cat 0.5 g vertical tubular reactor 98.0 87.0
0.3%Pd/CHT[5] 180 3.6 WHSV 2 h 1 Fixed bed reactor 41.0 97.0
11 1%Pd/HT-A[19b] 180 4.0 WHSV 0.037 mol h 1 g 1cat Vertical flow reactor 98.0 92.0
12 1%Pd/HT-F[19b] 180 4.0 WHSV 0.037 mol h 1 g 1cat Vertical flow reactor 94.0 93.0
13 1%Pd/Al2O3[11b] 230 5.4 cat 0.5 g; Fixed bed reactor 77.0 98.0
Phenol flow rate 0.0135 mol h 1
14 1%Pd/MgO[11b] 230 5.4 cat 0.5 g; Fixed bed reactor 90.0 82.0
15 Phenol flow rate 0.0135 mol h 1
[29]
16 Pd/F-MgO 300 5.4 WHSV 0.027 mol h 1 g 1cat Fixed bed reactor 54.0 80.0
Pd/AC[22] 150 - W/Fphenol 385 g mol 1 h Fixed bed reactor 55.0 90.0
17 Pd/Ta2O5[22] 150 - W/Fphenol 128 g mol 1 h Fixed bed reactor 54.0 87.0
18 Pd/graphite[22] 150 - W/Fphenol 192 g mol 1 h Fixed bed reactor 45.0 59.0
19 3%Pd/CeO2-MS[9a] 180 6.0 WHSV 23 mol h 1 kg 1cat Fixed bed reactor 93.7 47.0
3%Pd/ZrO2-MS[9a] 180 6.0 WHSV 23mol h 1 kg 1cat Fixed bed reactor 62.9 93.0
20 5%Pd/SiO2[26] 150 - W/Fphenol 128 g mol 1 h Fixed bed reactor 44.0 62.0
21 5%Pd Yb/SiO2[26] 150 - W/Fphenol 128 g mol 1 h Fixed bed reactor 69.0 68.0
22 1%Pd/TiO2[21] 200 4.5 cat 0.5 g; feed rate 2.5 ml h 1 Fixed bed reactor 79.6 99.0
Pd/HPS[10c] 120 - - Stainless steel tube 99.2 95.3
23 Rh/SBA-15[17] 180 6.0 cat 0.6 g; WHSV 27mol h 1 kg 1cat Fixed bed reactor 95.0 60.0
24 Rh/SBA-16[17] 180 6.0 cat 0.6 g; WHSV 27mol h 1 kg 1cat Fixed bed reactor 75.0 45.0
25 (Phenol Conv. represents the conversion of phenol; Cyclohexanone Sel. represents the selectivity of cyclohexanone; “*” represents the not-precise data)
26
27
28
29
30
31
32
33
34
35
36 Figure 3. Proposed phenol hydrogenation pathways in liquid phase (upper
37 route) and gas phase (lower route). Reproduced with permission from ref
[14]. Copyright 2014, American Chemical Society.
38
39
40
41 Scheme 1. Adsorption patterns of phenol and hydrogen. In contrast to that in liquid phase, the formed enol absorbed
42 on the catalyst strongly and would be further hydrogenated to
43 cyclohexanol because the keto/enol equilibrium was thermody-
44 of phenol and hydrogen (Scheme 1a ~ b).[5] The manner in namically unfavorable and kinetically hindered in gas phase.[14]
45 which the phenol was adsorbed depended on the strength and Generally, keto/enol isomerization was strongly influenced by
46 the amount of acid-base sites around the metal sites.[5] the aqueous environment and hence the activation energy of
47 In addition to the adsorption pattern of the reactants, the isomerization reaction in aqueous solution was appreciably
48 environment in which the phenol hydrogenation proceeds, i. e., lower than that in vapor phase. The major effect of the liquid
49 gas-phase or liquid-phase, may lead to different reaction path was to influence the energy of charged surface bound
50 and product distribution. For example, Yoon and coworkers intermediates, resulting in the preferential formation of
51 carried out a first-principle study of phenol hydrogenation ketones. Considering the fact that the reaction routes and
52 recently by setting different amounts of H2O molecules to prerequisites for catalysts were different under different reac-
53 create vapor and liquid conditions (Figure 3).[14] According to tion conditions, the catalysts used in gas-phase and liquid-
54 the calculated results, phenol was hydrogenated to cyclo- phase hydrogenation of phenol were summarized and classi-
55 hexadienol in both circumstances. In liquid phase, the pro- fied, respectively.
56 duced enol passed through a rapidly isomerization to produce
57 3-cyclohexenone and further hydrogenated to cyclohexanone.
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1 3. Gas-phase Hydrogenation of Phenol demonstrated that Pd/HPS (hypercrosslinked polystyrene) was
2 a promising catalyst for industrial hydrogenation of phenol due
3 Despite requiring high reaction temperature, gas-phase hydro- to its comparable activity and selectivity with that of commer-
4 genation of phenol possesses many merits such as continuous cial Pd/Al2O3 catalyst (conv. 99%, sel. > 95%). Beyond that, the
5 manipulation, in situ activation of used catalysts, no filtering cyclohexanone yield in Pd/HPS catalyst was at least 2–3%
6 and separating steps, and etc. In the past few decades, gas- higher than that in commercial Pd/Al2O3 at higher reaction
7 phase hydrogenation of phenol was studied over a range of temperatures (160-180 8C).[10c] Scirè et al. reported that the order
8 noble-metal catalysts including Pt, Pd and Rh as well as non- of catalysts in terms of catalytic activity and cyclohexanone
9 noble metal Ni-based catalysts (Table 1). Especially for Pd-based selectivity followed the sequence of Pd/La2O3 > Pd/CeO2 > Pd/
10 catalysts, the impact of supports, modifiers and precursors was Al2O3 while the acidity of the supports was in the reverse order,
11 all investigated in detail. indicating that the lower the acidity of the support was, the
12 higher the catalytic activity of phenol and selectivity to cyclo-
13 hexanone were.[20] The catalytic activity of Pd supported on
14 3.1. Noble Metal Catalysts mesoporous CeO2 (Pd/CeO2-MS) and ZrO2 (Pd/ZrO2-MS) were
15 evaluated in vapor-phase hydrogenation of phenol by Velu and
16 In 1970s, gas-phase hydrogenation of phenol was carried out coworkers in 2003. They proposed that the acid-base property
17 over Pt-based catalysts which exhibited high catalytic activity.[15] of supports determined the adsorption manner of phenol. In
18 However, cyclohexanol instead of cyclohexanone was formed Pd/CeO2-MS case, unsaturated Ce4 + ions acted as Lewis acid
19 predominantly.[16] Among the reported noble metal catalysts, sites, phenol adsorbed on Lewis acid sites in a co-planar
20 Pd-based catalyst was declared with the best performance in manner would generate a mixture of cyclohexanone, cyclo-
21 phenol hydrogenation when the selectivity of cyclohexanone hexanol and cyclohexane (Scheme 2a). However, due to the
22 and production cost were taken into consideration.[16] Com-
23 pared with Pd and Pt, Rh is less reported as a catalyst in the
24 field of selective hydrogenation of phenol due to its high cost
25 and relatively general catalytic performance.[17] It is well-known
26 that the catalytic performance is intimately related to the
27 choice of supports, promoters and metal precursors. We will
28 briefly summarize the application of catalysts for gas-phase
29 hydrogenation of phenol in the three aspects.
30
31
32 3.1.1. Supports
33
34 Support materials decide both the activity and selectivity for a
35 Metal/Support type catalyst in a certain degree. This theory Scheme 2. The two adsorption patterns of phenol give rise to different
products. Reproduced with permission from ref [9a]. Copyright 2003,
36 perfectly works in phenol hydrogenation reactions.[18] Not only Elsevier.
37 do the acid-base property of supports but also the interaction
38 between metal particles and supports have great effects on
39 catalytic performance. amount of basic sites exsited on Pd/ZrO2-MS, phenol absorbed
40 MgO and Al2O3 were frequently applied as supports in on basic sites in a non-planar fashion led to the predominant
41 vapor-phase hydrogenation of phenol. Neri et al. found that Pd/ product being cyclohexanone (Scheme 2b).[9a] Sikhwivhilu et al.
42 MgO was superior to Pd/Al2O3 in terms of stability and studied the catalytic performance of Pd/TiO2 in gas-phase
43 cyclohexanone selectivity.[3a] The authors put forward the theory hydrogenation of phenol. Extending the aging time of TiO2 in
44 of “two-site” adsorption in this work, i. e., hydrogen activated the KOH solution resulted in an increase of basic sites and
45 on noble metals reacted with phenol molecule adsorbed on different tubular structures of TiO2, phenol non-planar adsorbed
46 the oxides surface near Pd particles.[3a] Yet, MgO-supported on basic sites of TiO2 with large BET surface area resulted in the
47 catalysts are not reputed for large-scale commercial applica- main product being cyclyhexanone.[21] Thus, it can be seen that
48 tions owing to their poor mechanical strength. Al2O3-supported the acid-base property of supports plays an important role in
49 catalysts are generally applied in industry but they suffer from the gas-phase hydrogenation of phenol by affecting the
50 severe deactivation as the reaction proceeds because lots of adsorption manner of the reactants.
51 acid sites on Al2O3 can cause the carbon deposition easily. To Beyond doubt, the interaction between metal and support
52 bridge the gap, some scientists tried to combine the advan- also affects the catalytic performance. The specific activities
53 tages of MgO and Al2O3.[5] For example, Narayanan and cow- among plenty of Pd-based catalysts exhibited the following
54 orkers prepared hydrotalcite supported Pd catalysts (Pd/HT). order in Park’s work: Pd/AC < Pd/GCN (graphitic carbon nano-
55 They found that the Pd/HT catalysts were highly selective for fibers) < Pd/SiO2 ~ Pd/graphite < Pd/Ta2O5.[22] The different activ-
56 phenol hydrogenation (~ 90% selectivity of cyclohexanone) ity was ascribed to the different interaction between metal sites
57 with a phenol conversion greater than 95%.[19] Sulman et al. and various supports, which influenced the microstructure of
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1 Pd such as particle size distribution, particle geometry, and activating hydrogen, leading to an increased activity. Secondly,
2 electronic characters.[22] The fast intrinsic reaction rate existed in alkali metals poisoned the Lewis acid sites of the Al2O3, then
3 those systems exhibiting strong metal support interactions promoted the non-planar adsorption of phenol and gave rise to
4 (SMSI). As is known, SMSI is beneficial for the dispersion of the yield of cyclohexanone. Thirdly, alkali metals facilitated to
5 active sites, while Chary’s work showed an inverse relationship desorb cyclohexanone by decreasing the interaction between
6 between the dispersion of Pd and hydrogenation activity of Pd/ cyclohexanone and the support. Both the second and the third
7 C catalysts for phenol hydrogenation.[23] That is to say, too aspects caused an increased selectivity of ketones.[3a,24] Mahata
8 strong interaction may be not beneficial for phenol hydro- et al. proposed a reaction mechanism that the interaction
9 genation. In general, appropriate interaction (neither strong nor between the positively charged promoting ion and oxygen
10 weak) between metal site and support is conducive to the gas- atom of the phenolate could decrease the bonding strength
11 phase hydrogenation of phenol. between the adsorbed phenol and support, thereby stimulating
12 Similar to Pd-based catalysts, the choice of supports largely the desorption of products and resulting in an enhanced
13 determines the product distribution over Rh-based catalysts. selectivity of cyclohexanone (Scheme 3).[18] Mahata et al. further
14 The Rh/CNF (carbon nanofiber) catalyst prepared by Wang and
15 coworkers presented a high reactivity for phenol hydrogenation
16 in scCO2 system even at a low temperature of 323 K.[10a] The
17 cyclohexaone selectivity of Rh/CNF was higher than that of Rh/
18 C catalyst, denoting that the capability of catalysts depended
19 on the support materials used.[10a] Giraldo and coworkers
20 investigated the catalytic activity of Rh supported on meso-
21 porous silica (SBA-15 and SBA-16).[17] The reason why Rh/SBA-15
22 exhibited a higher conversion of phenol than Rh/SBA-16 was
23 that the higher Ru dispersion endowed SBA-15 with more
24 exposed active sites, and the special structure of Rh/SBA-15
25 allowed reactants to penetrate inside the structure (Figure 4).
26
27
28 Scheme 3. The reaction mechanism of promoter ion in Pd/Al2O3 catalyst.
29 Reproduced with permission from ref [18]. Copyright 1999, Elsevier.
30
31
32 explored the correlation between the activity of catalysts and
33 the charge transfer capacity (CTC) of alkali and alkaline earth
34 metals additives over Pd/Al2O3 catalysts system. The electron
35 density of active sites increased with the increasing CTC of
36 alkaline dopants, which resulted in an improvement of phenol
37 conversion without affecting the product selectivity.[25] Shore
Figure 4. Reaction diagram between phenol and (a) SBA-15, (b) SBA-16.
38 Reproduced with permission from ref [17]. Copyright 2014, Multidisciplinary and coworkers found that lanthanides can also act as
39 Digital Publishing Institute. promoters in Pd-based catalysts. They deemed that the hydro-
40 gen transferred from Yb hydride to Pd0 boosted the hydro-
41 genation rate.[26] For Pt-based catalysts, introducing a second
42 Oppositly, the cyclohexanone selectivity of Rh/SBA-16 was metal can act the same effect as the doping of alkaline
43 higher than that of Rh/SBA-15 catalyst. The variation in additives in Pd-based catalysts in terms of altering the product
44 selectivity might be owing to the structure property of catalysts distribution and achieving high selectivity of cyclohexanone.
45 and the adsorption mechanism of phenol.[17] Srinivas et al. concluded that Pt Cr/C alloy catalyst afforded a
46 better selectivity of cyclohexanone than Pt/C. They supposed
47 that the improved selectivity of cyclohexanone in alloy catalysts
48 3.1.2. Additives was attributed to the dilution effect of Cr on the Pt sites, which
49 accelerated the dissipation of the reaction heat. Moreover, Cr
50 Except for the transition metals and supports, a third could inhibit the occurrence of side reactions by selectively
51 component refers to as additives, always emerges in heteroge- blocking the surface sites.[7a,27] The authors further investigated
52 neous catalysts. The additives have a positive effect on the the catalytic performance of Pt M/C (M = Cr, V and Zr) alloy
53 performance of catalysts in aspects of activity, selectivity and catalysts for phenol hydrogenation. The relatively high selectiv-
54 stability.[2c] ity of cyclohexanone was obtained in Pt Cr/C and Pt V/C
55 Neri et al. divided the impacts of alkaline promoters (K, Ca, catalytic systems, and in contrast, cyclohexanol was the main
56 Cs) into three aspects. Firstly, alkali metals modified the product in Pt Zr/C catalytic system. The different interaction
57 electronic surrounding of metallic Pd, which was beneficial for between Pt and the second metal (Cr, V and Zr), affecting the
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1 electronic state of Pt and its affinity for reactants, was supposed produce cyclohexanone/cyclohexanol via the hydrogenation
2 to be the main reason for the selectivity distinctions.[27b,28] route, while benzene was generated through hydrogenolysis
3 pathway when methanolic solution of phenol (phenol dissolved
4 in methanol solution) was fed.[32] In addition, doping of
5 3.1.3. Precursors promoters (Yb, alkali and alkaline promoters) over Ni-based
6 catalysts could suppress the hydrogenolysis of phenol, but the
7 There is no doubt that the precursors play a considerable role Ni metal tended to hydrogenate phenol completely to cyclo-
8 in the property of final catalyst including metal dispersion, hexanol due to the electron transferred from promoters to Ni
9 particle size distribution and thus the catalytic performance. active sites.[25–26] Hu’s work showed that the Ni-based catalysts
10 A systematic study was carried out by Mahata and co- possessing higher active nickel surface area could be obtained
11 workers about the influence of the Pd precursors.24 As revealed by treatment with n-butanol solution during the drying process
12 by their results, the Pd dispersion depended strongly on both of catalyst preparation, which was more active in the aromatic
13 the precursor-support interaction and the size of precursor ring hydrogenation of phenol.[33]
14 ions. The reason why Pd(OOCCH3)2 offered a better dispersion
15 of Pd than PdCl2 or Pd(NH3)4Cl2 was that the large counter
16 anion in acetate precursors separated the metal anion apart. A 4. Liquid-phase Hydrogenation of Phenol
17 fraction of chlorine was retained in the catalysts prepared from
18 chlorinated precursors (PdCl2 and Pd(NH3)4Cl2). The residue Gas-phase hydrogenation of phenol should be reacted at a
19 chlorine would decrease the hydrogenation activity of those relatively high temperature, which leads to a fast deactivation
20 catalysts by decreasing the charge density of metal sites. The of catalyst. Thus, liquid-phase hydrogenation of phenol comes
21 surface migration of metal chloride in the metal particles or at into research focus due to its mild conditions and energy
22 the metal-support interface gave rise to the larger Pd particles. saving. Pd is still the most widely used noble metal for phenol
23 Not only did the residue chlorine but the presence of inherent hydrogenation among transition metals thanks to its good
24 NH3 (auto-reduction and surface migration) made against the selectivity of cyclohexanone. Here we summarize the catalysts
25 high dispersion of Pd when Pd(NH3)4Cl2 used as the metal used for liquid-phase hydrogenation of phenol by classifying
26 precursor.[11b,29] Scirè et al. studied the relationship between the support types (Table 2). The catalysts used for in situ
27 precursor and product selectivity. They found that a higher hydrogenation process were also listed.
28 selectivity of cyclohexanone could be obtained on the catalysts
29 prepared from Pd(OOCCH3)2 than that on the catalysts prepared
30 from PdCl2.[20] 4.1. Carbon Materials
31
32 Carbon materials, characterized with numerous fascinating
33 3.2. Non-noble Metal Catalysts properties including high specific surface area, large pore
34 volume, thermal conductivity and low cost of manufacture, are
35 From the viewpoints of cost and sustainable chemistry, non- ideal candidates as catalyst supports.[35] Pd/C catalysts are
36 noble transition metals show better promise than noble metals. widely used to catalyze phenol hydrogenation under relatively
37 Ni is one of the most intensively studied and best performed mild conditions in liquid phase, but unmodified Pd/C catalysts
38 non-noble metals for hydrogenation reaction. However, the have a poor selectivity towards cyclohexanone. Other catalyst
39 selectivity of cyclohexanone was general over the Ni-based systems, such as Pt/C, Ru/C and Rh/C, do not work for large-
40 catalysts for gas-phase hydrogenation of phenol.[30] scale applications because of some practical disadvantages
41 Phenol tends to undergo hydrogenolysis instead of hydro- including the need of harsh reaction conditions, low conversion
42 genation reaction on unmodified Ni-based catalysts prepared and low selectivity. To fill these pitfalls mentioned above, some
43 by traditional method.[31] To design a Ni-based catalyst combin- attempts through modifying the supports or changing the
44 ing the feature of promoting phenol hydrogenation and reaction environments were taken into consideration.
45 inhibiting the hydrogenolysis process together will expand the
46 application of non-noble metal catalysts in gas-phase hydro-
47 genation of phenol. There are many factors such as Ni loadings, 4.1.1. Modification of Supports
48 reaction temperature, solutions, doping of heteroatoms and
49 preparation method can affect the reaction pathway of phenol For carbon materials-supported catalysts, the hydrophilicity/
50 hydrogenation over Ni-based catalysts. hydrophobicity determine the product distribution in the
51 Shin et al. investigated the Ni/SiO2 and Ni/Na Y catalysts for hydrogenation reaction of phenol, which can be modified by
52 the gas-phase hydrogenation/hydrogenolysis of phenol. The the oxidation treatment or introducing the nitrogen compo-
53 pathway concerning the hydrogenolysis of phenol to benzene nents.
54 and then hydrogenation to cyclohexane was favored over the For phenol hydrogenation, approximate 95% yield of cyclo-
55 catalyst bearing a high Ni loading under elevated temperatures. hexanone was obtained on Pd@hydrophilic-C while 0% selectiv-
56 They put forward that, by using phenol aqueous solution feed ity of cyclohexanone was achieved in 10%Pd@C catalyst under
57 (phenol dissolved in water), phenol probably preferred to same reaction conditions.[37] The authors speculated that
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Table 2. Summary of catalysts for phenol hydrogenation in liquid phase.
Catalyst Solvent T(oC) PH2(MPa) Time Experimental Reactor Phenol Conv. Cyclohexanone
(h) Parameters (%) Sel. (%)
Pd/mpg-C3N4[3c] H2O 65 0.1 2.0 Pd/phenol 5 mol% Flask > 99 > 99

5%Rh/C[10d] scCO2 55 10 2.0 Initial phenol 0.02 mol Reactor 87.0 34.0
5%Rh/CNF[10a] scCO2 50 4.0 0.5 cat 50 mg; phenol 1 g Batch 100 43.3
Pd@hydrophilic-C[37] H2O 100 1.0 20 cat 50 mg; phenol 100 mg Autoclave > 99 95.0
ChemNanoMat 2018, 4, 1 – 20
5.0 mol%Pd/MCN@MS- H2O 80 0.1 3.0 cat 80 mg; phenol 0.5 mmol Flask > 99 99.0
NH2[39]
5%Pd/C-AlCl3[3b] CH2Cl2 50 1.0 7.0 Pd/phenol 5 mol% Reactor > 99 > 99
5%Pd/Al2O3-AlCl3[3b] CH2Cl2 30 1.0 8.0 Pd/phenol 5 mol% Reactor > 99 > 99
2.5%Pd/NaY-AlCl3[3b] CH2Cl2 50 1.0 4.0 Pd/phenol 5 mol% Reactor > 99 > 99
5%Pd/C-InCl3[3b] CH2Cl2 30 1.0 16 Pd/phenol 5 mol% Reactor > 99 > 99
5%Pd/C-ZnCl2[3b] CH2Cl2 30 1.0 20 Pd/phenol 5 mol% Reactor > 99 > 99
5%Pd/C-SnCl2[3b] CH2Cl2 30 1.0 22 Pd/phenol 5 mol% Reactor > 99 > 99
5%Pd/C[72a] NaOH 150 0.5 - cat 190 mg; phenol 90 mg - 61.0 95.7
5%Pd/C-A[72a] NaOH 150 0.5 - cat 190 mg; phenol 90 mg - 40.0 98.2
5%Pd/C-AN[72a] NaOH 150 0.5 - cat 190 mg; phenol 90 mg - 16.0 99.0
10%Pd/C[10b] HCOONa + H2O 80 2.0 0.25 cat 5.3 mg; phenol 0.625 mmol Batch reactor 100 98.1
10%Pd-PANI/CNT[9b] H2O 80 0.1 9.0 Pd/phenol 5 mol% Flask > 99 > 99
www.chemnanomat.org
10%Pd-PANI/CNF[9b] H2O 80 0.1 9.0 Pd/phenol 5 mol% Flask > 99 > 99
10%Pd-PANI/CB[9b] H2O 80 0.1 9.0 Pd/phenol 5 mol% Flask > 99 > 99
Pd@mpg-C3N4[3d] H2O 65 0.1 6.0 Pd/phenol 4 mol% Flask 100 100
3%Pd/CNTs[36] CH3OH + H2O 220 3.5 MPa Ar - cat 0.5 g; Cphenol 0.2 mol L 1 Tubular reactor 60.1 81.6
LHSV 3.87 h 1
3%Ni/CNTs[36] CH3OH + H2O 220 3.5 MPa Ar - cat 0.5 g; Cphenol 0.2 mol L 1 Tubular reactor 37.3 24.3
8
LHSV 3.87 h 1

3%Pd/ACs[36] CH3OH + H2O 220 3.5 MPa Ar - cat 0.5 g; Cphenol 0.2 mol L 1 Tubular reactor 2.9 95.6
LHSV 3.87 h 1
3%Ni/ACs[36] CH3OH + H2O 220 3.5 MPa Ar - cat 0.5 g; Cphenol 0.2 mol L 1 Tubular reactor 3.2 41.0
LHSV 3.87 h 1
Pd@CN[40] H2O 45 0.1 4.0 Pd/phenol 4 mol% Flask 100 99.0
4.3%Pd/AC[83] H2O 50 0.5 4.0 cat 100 mg; phenol 2.5 mmol Batch reactor 98.3 66.4
4.9%Pd/MIL-101[83] H2O 50 0.5 4.0 cat 100 mg; phenol 2.5 mmol Batch reactor 99.6 80.3
4.3%Pd/AC[83] H2O + HCOOH 50 0.3 MPa N2 4.0 cat 100 mg; phenol 2.5 mmol; Batch reactor 66.5 96.3
formic acid 400 uL
4.9%Pd/MIL-101[83] H2O + HCOOH 50 0.3 MPa N2 4.0 cat 100 mg; phenol 2.5 mmol; Batch reactor 47.3 96.4
formic acid 400 uL
[41a]
5%Pd/CN-3 H2O 80 1.0 1.0 cat 0.04 g; phenol 1.0 g Autoclave 64.0 94.9
5%Pd/CN-0[41a] H2O 100 2.0 4.0 cat 0.04 g; phenol 1.0 g Autoclave 99.5 67.1
5%Pd/CN-8[41a] H2O 100 2.0 4.0 cat 0.04 g; phenol 1.0 g Autoclave 66.5 78.8
Pd/CNTs[38] H2O 80 1.0 0.67 cat 0.1 g; phenol 0.2 g Autoclave > 99.9 24.4
Pd/OCNTs[38] H2O 80 1.0 0.5 cat 0.1 g; phenol 0.2 g Autoclave > 99.9 71.2
Pd/OCNTs-HT[38] H2O 80 1.0 0.5 cat 0.1 g; phenol 0.2 g Autoclave > 99.9 0.00
Pd/OCNTs-Air[38] H2O 80 1.0 0.5 cat 0.1 g; phenol 0.2 g Autoclave > 99.9 87.3
Annealed Pd/CNT[95] H2O 80 0.1 1.0 cat 10 mg; phenol 0.5 mmol Flask 7.20 100
Pd/CNT-GO-HNO3-treat[95] H2O 80 0.1 1.0 cat 10 mg; phenol 0.5mmol Flask 50.3 95.6
Pd/800N-AC[41b] H2O 40 0.3 6.0 cat 20 mg; phenol 0.2 mmol Autoclave 98.4 93.0
Raney Ni + Hbeta(60)[96] H2O + CH3OH 220 1 MPa N2 4.0 cat 1.0 g; phenol 3.0 g; Batch reactor 100 24.5
zeolite solid acid 0.1 g
Raney Ni + HZSM-5(25)[96] H2O + CH3OH 220 1 MPa N2 4.0 cat 1.0 g; phenol 3.0 g; Batch reactor 99 1.20
zeolite solid acid 0.1 g
Focus Review
3%Pt-in/CNTs[97] CH2Cl2 50 0.5 0.5 cat 20 mg; phenol 0.5 g Autoclave 97.3 77.5
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3%Pt-out/CNTs[97] CH2Cl2 50 0.5 0.5 cat 20 mg; phenol 0.5 g Autoclave 11.6 72.3
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Table 2. continued
Catalyst Solvent T(oC) PH2(MPa) Time Experimental Reactor Phenol Conv. Cyclohexanone
(h) Parameters (%) Sel. (%)
3.55%Pd@CN[41c] H2O 80 0.1 1.0 cat 0.1 g; Schlenk tube 96.9 94.1
1wt%phenol aqueous solution 5 mL
Pd/C[46] CH3COOH + H2O 100 1.0 2.0 cat 25 mg; phenol 1 g Autoclave 61.0 91.0
Ru/Al2O3[53] cyclohexane 160 5.0 2.0 Ru metal 2 mg; phenol 10 g Autoclave 81.5 87.0
ChemNanoMat 2018, 4, 1 – 20
Pd/Al2O3-CWE[58] H2O 100 0.5 0.83 cat 188 mg; phenol 100 mg Batch reactor 100 98.0
Pd/Fu-TiO2-C[59] H2O 100 0.5 - Pd/phenol 5 mol% Batch reactor 99.0 97.0
Pd/Fu-TiO2-C-C[59] H2O 100 0.5 - Pd/phenol 5 mol% Batch reactor 99.0 9.0
Pd/TiO2-ACZnCl2[59] H2O 100 0.5 - Pd/phenol 5 mol% Batch reactor 99.0 96.0
Pd/Al2O3-3 nm[50] H2O 60 0.1 3.0 Pd/phenol 2.3 mol% Flask > 99 > 99
Pd/SiO2-3 nm[50] H2O 60 0.1 7.5 Pd/phenol 2 mol% Flask 99 97.0
Pd@sMMT-1[61] H2O 35 0.1 15 Pd/phenol 1.5% > 99 98.0
3.12%Pd/MS-C3@MS-NH2[62] H2O 80 0.1 3.0 cat 80 mg; phenol 0.5 mmol Vessel 98.5 97.0
Pd/MSN[55] CH2Cl2 50 1.0 1.0 m(Pd)/m(phenol) = 1 : 500 Autoclave 12.2 92.6
PdRu/MSN[55] CH2Cl2 50 1.0 1.0 m(Pd)/m(phenol) = 1 : 500 Autoclave 71.7 62.6
Pt/TNT[60] CH2Cl2 50 0.5 0.5 cat 20 mg; phenol 0.5 g Autoclave 46.0 90.0
Pt@TNT[60] CH2Cl2 50 0.5 0.5 cat 20 mg; phenol 0.5 g Autoclave 96.0 90.0
Pd/CeO2[68] Hexane 25 0.1 4.0 Pd/phenol 5 mol% Flask 86.2 96.3
www.chemnanomat.org
1%Ru/Al2O3[52] cyclohexane 80 0.2 1.0 cat 50 mg; phenol 500 mg Batch reactor 82.1 67.9
0.5%Pd/SiO2[98] CH3CH2OH 135 1.0 - cat 1 g; Autoclave 71.6 90.7
ethanol phenol (mass ratio 1 : 4) 20 ml
K-Pd/TiO2[57] H2O 80 0.06 10 Pd/phenol 0.44 mol% Batch reactor > 99 > 99
Na-Pd/TiO2[57] H2O 80 0.06 10 Pd/phenol 0.44 mol% Batch reactor > 99 > 99
Rh/SBA-15[99] – 60 1.2 MPa H2 + 11 MPa 1.0 cat 3 mol%Rh; phenol 0.015 g Reactor 100 20.0
9
CO2

Pd/C-Sc(OTf)3[100] CH2Cl2 20 0.1 2.0 Pd 10 mol%; phenol 0.5 mmol – > 99 > 99
Pd/A-HPW[75] H2O 80 0.1 7.0 Pd/phenol 5 mol%; Flask > 99 > 99
Pd/PVP[76] H2O 90 0.1 16 Pd/phenol 5 mol%; Round bottle 99.5 99.7
H2PdCl4/PVP/NaBH4 1 : 20 : 7
Pd/A-45[77] H2O 100 1.0 0.5 phenol 0.5 mmol; phenol/Pd = 8.0 Autoclave 100 89.0
4.9%Pd/MIL-101[71] H2O 50 0.5 2.0 Pd/phenol = 1.9 mol% Batch reactor 85.0 98.8
5%Ru/MIL-101[70] H2O 50 0.5 4.0 cat 100 mg; phenol 235 mg Batch reactor 90.0 90.0
Pd/La1-Al2O3[84] H2O + methol 217 3.5 MPa Ar - phenol/methanol/water Fixed-bed reac- 44.4 96.3
(molar ratio) 1 : 20 : 80 tor
Pd/Al2O3[82] H2O + ethanol 217 3.5 MPa Ar - LHSV 3.5 h 1; substrate/alcohol/water (molar ratio) Tubular reactor 40.4 92.4
1 : 20 : 80
[78]
Ru@NaX H2O 80 0.1 11 cat 50 mg, phenol 100 mg Flask 99.9 95.4
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Focus Review
1 phenol was adsorbed on the hydrophilic-C more strongly than philic shell) in the silica framework stabilized the Pd NPs
2 cyclohexanone because cyclohexanone was hydrophobic spe- effectively.[39]
3 cie. Consequently, cyclohexanone was easily replaced by a new Chemical doping with foreign atoms is also proved to be an
4 phenol molecule, avoiding the further hydrogenation to effective method to manipulate surface property of host
5 generate cyclohexanol. Nitric acid treatment of CNTs and ACs materials. Nitrogen-doping has been the most intensive
6 increased the hydrophilicity of these carbon materials by research direction during the past decades.[35a] Recently, the
7 generating more oxygen-containing groups.[36] The effect of theory confirmed in phenol hydrogenation for the first time by
8 support surface property on the adsorption/desorption of our group was that the basic sites introduced into the carbon
9 substance was probed via DFT theoretical calculation by Xiang material by doping with N can lead to an enhanced interaction
10 and coworkers.[36] The results demonstrated that phenol between the carbon surface and acidic molecules.[3c] The mpg-
11 adsorbed more strongly at the interface between Pd and C3N4 (mesoporous graphitic carbon nitride), a kind of carbon
12 oxidized CNTs or ACs than adsorbed on the Pd surface material containing 60 wt% N, can effectively improve the
13 (Figure 5). Meanwhile, cyclohexanone desorbed from the hydro- activity and selectivity of phenol hydrogenation reaction.
14 Almost complete conversion of phenol with > 99% selectivity
15 of cyclohexanone was obtained even under mild reaction
16 conditions of 65 8C for 2 h and atmospheric pressure in aqueous
17 solution. The excellent catalytic performance could be attrib-
18 uted to the addition of N, which wasthat phenol adsorbed on
19 the surface of mpg-C3N4 in a non-planar fashion through the
20 hydroxyl group via weak O H···N or O H···p interactions
21 (Scheme 4), giving rise to the enhanced catalytic activity for
22
23
24
25
26
27
28 Figure 5. Side and top view of CNTs with adsorbed (a) hydroxyl and oxygen
29 (b) hydroxyl groups. The adsorption energy of water, methanol, phenol, and Scheme 4. Possible reaction mechanism of Pd@mpg-C3N4 in phenol hydro-
cyclohexanone on the completely hydrophilic (site 1), partially hydrophilic genation. Reproduced with permission from ref [3c]. Copyright 2011,
30 American Chemical Society.
(site 2), and completely hydrophobic (site 3) regions of CNTs with adsorbed
31 (c) hydroxyl and oxygen and (d) hydroxyl groups. Reproduced with
32 permission from ref [36]. Copyright 2014, American Chemical Society.
33 phenol hydrogenation. On the other hand, the N contained in
34 mpg-C3N4 resulted in not only a very stable and uniform
35 philic surface easily. The different interaction of phenol and dispersion of Pd with high proportions of Pd0 on the surface of
36 cyclohexanone with hydrophilic surface finally led to the major the catalyst (70%) but also the additional electronic activation
37 product being cyclohexanone. However, Xu and coworkers of the Pd NPs.[3c,d] Our following study proved that the Pd/CN-1
38 found that the increasing of C O content, i. e., the increasing of catalyst with a lower N content (11.98%), which was synthesized
39 hydrophilic, had a positive impact on dispersion of Pd particles by using ionic liquids as precursors and Ludox HS-40 colloidal
40 but had a negative effect on the selectivity of cyclohexanone.[38] silica as the hard template, could achieve the same catalytic
41 Specifically, the strong interaction between Pd precursor and performance for phenol hydrogenation as the mpg-C3N4 with N
42 carbon support containing many C O groups could promote content of nearly 60 wt%.[40] Afterwards, many different kinds of
43 the dispersion of Pd. Oppositely, they thought that the nitrogen-doped carbon materials were taken to support
44 strong interaction between C O groups in catalyst surface transition metals and applied in phenol hydrogenation, which
45 and the C=O groups in cyclohexanone might cause the showed the elevated catalytic reactivity exceeded that of
46 further hydrogenation of cyclohexanone to cyclohexanol.[38] nitrogen-free carbons.[9b,41]
47 Zhang et al. prepared Pd/MCN@MS-NH2 catalyst with hydro-
48 phobic carbon core and hydrophilic silica shell. The Pd/MCN
49 and Pd/MS-NH2 were prepared as control catalysts. A > 99% 4.1.2. Adjustment of Reaction Environments
50 phenol conversion with 99% cyclohexanone selectivity was
51 achieved over Pd/MCN@MS-NH2 catalyst, while Pd/MCN and In liquid-phase reactions, solvents have pronounced effects on
52 Pd/MS-NH2 obtained phenol conversion just of 83.3% and reaction equilibrium. Solvents influence the reaction rate and
53 77.9% under the same reaction condition, respectively. It mechanism not only by altering the solubility, mass transfer
54 would be explained for the good catalytic performance of and the sorption behavior of reactants but also via interacting
55 Pd/MCN@MS-NH2 by the synergy of hydrophobic core and with catalysts.
56 hydrophilic shell. The MCN (hydrophobic core) played an H2O In recent years, H2O has become a popular solvent for
57 important role in enriching substrates and the -NH2 (hydro- phenol hydrogenation because it helps catalysts get better
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Focus Review
1 activity and cyclohexanone selectivity. Yoon and coworkers
2 found that the liquid-phase surroundings reduced the work
3 function of metal according to the DFT electronic-structure
4 calculations.[14] They considered that the addition of H adatom
5 was a neutral H atom transfer (not a proton H + or a hydride H
6 transfer) both in gas and liquid phase, thus, the influence of
7 water on the reaction energy barriers for phenol hydrogenation
8 was very weak. However, keto/enol isomerization was strongly
9 influenced by the aqueous environment, and hence, the
10 activation energy of isomerization reaction in aqueous solution
11 was appreciably lower than that in vapor phase. Sum up, the
12 major effect of the liquid was to influence the energy of Scheme 6. Possible reaction mechanism of phenol hydrogenation under
13 charged surface bounding intermediates, leading to the deuterium oxide. Reproduced with permission from ref [3d]. Copyright 2013,
The Royal Society of Chemistry.
14 preferential formation of cyclohexanone during phenol hydro-
15 genation reactions. The similar results also appeared in the DFT
16 calculation of our group’s work, i. e., the presence of H2O
17 molecule significantly decreased the activation energy of the scCO2.[10d] The turnover number (TON) of different catalysts
18 proton transfer reaction from 221.4 kJ mol 1 to 85.5 kJ mol 1.[3d] followed the sequence of Rh > Ru > Pd > Pt. The authors
19 Furthermore, our group found that H2O would participate in deemed that the Rh NPs with low electron density caused by
20 the reaction of phenol hydrogenation. Based on the isotopic electron transfer from Rh to CO2 could adsorb phenol strongly,
21 tracing study, we found that the phenol molecule exchanged leading to a relatively high TON of Rh-based catalysts. While the
22 deuterium with the D2O, resulting in the formation of cyclo- Pd NPs have higher affinity for CO2 than other metals, and the
23 hexanone containing a deuterium atom (GC-MS detected the competing adsorption between CO2 molecule and phenol
24 ionic peak with m/z = 99). Moreover, several ionic peaks with molecule on Pd NPs surface resulted in a lower catalytic activity
25 higher m/z (100 ~ 102) belonging to the cyclohexanone were of Pd-based catalyst than that of Rh and Ru-based catalysts. For
26 also detected and we attributed this phenomenon to the selectivity, the experiments showed that the dilution effect of
27 resonance and the H D exchange reaction in the reaction CO2 for H2 under high CO2 pressure would reduce the
28 systems (Scheme 5). After that, we found the existence of ionic possibility of hydrogenating phenol to cyclohexanol.[10d] Hitzler
29 et al. found the same effect in scCO2 conditions and they
30 attributed the improved reaction rate in scCO2 to both the
31 larger diffusion coefficient of phenol and the higher miscibility
32 of gaseous H2 with CO2.[43] In opposite, Fujita et al. declared that
33 the presence of CO2 reduced the hydrogenation rate of both
34 phenol and cyclohexanone. This negative effect was ascribed to
35 the formation and adsorption of CO on Rh/C catalyst at high
36 CO2 pressures with the presence of H2.[44] Generally, cyclo-
37 hexanol can be obtained by two pathways including direct
38 conversion of phenol and hydrogenation of cyclohexanone,
39 Fujita and coworkers proposed that the presence of CO2
40 retarded the second path but had no influence on the first
41 Scheme 5. Deuterium atoms locate on the adjacent position of the cyclo- because CO2 had molecular interaction with cyclohexanone
42 hexanone through a resonance and proton exchange route. Reproduced instead of phenol.[45]
with permission from ref [3d]. Copyright 2013, The Royal Society of
43 Chemistry. Acidic/basic solutions In 2009, Han et al. reported that the
44 synergy between Pd-based catalysts and Lewis acid (AlCl3, SnCl2
45 and ZnCl2) would generate good catalytic performance for
46 peaks with m/z = 103 ~ 105 and guessed that the activated H phenol hydrogenation under relatively mild conditions. In the
47 atom from H2 was exchanged with D in D2O, then the D atoms dual catalyst systems, the combination of the activation of
48 could be located on the products via the following hydro- benzene ring of phenol on Lewis acid coordination with the
49 genation process. This discovery also proved the proposal that activation of H2 on Pd NPs formed cyclohexanone quickly. At
50 H2 was activated on the metal sites.[3d] The total description of the same time, the acid-base interaction between the Lewis
51 the possible reaction mechanism was shown in Scheme 6. acid and cyclohexanone (Lewis base) inhibited the further
52 Supercritical carbon dioxide As one of the most widely hydrogenation of cyclohexanone to cyclohexanol (Scheme 7).[3b]
53 used solvent systems, supercritical carbon dioxide (scCO2) can Very recently, our group explored the reaction mechanism of
54 increase the reaction rate because of the infinite miscibility of phenol hydrogenation at acidic and basic solutions by combin-
55 H2 with CO2, which eliminated the transfer resistance on gas- ing experiments and DFT calculations.[46] In basic solution, the
56 liquid interface.[42] Rode and coworkers investigated a series of decreased activity was attributed to the generation of pheno-
57 charcoal-supported catalysts for phenol hydrogenation in late caused by the integration of phenol with the OH ions of
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Focus Review
1 4.2. Oxides
2
3 Due to the robust mechanical and chemical stabilities as well as
4 the tunable surface properties, oxides are another kind of the
5 most frequently applied supports for liquid-phase hydrogena-
6 tion of phenol.[47]
7 Same as the gas-phase hydrogenation, Al2O3 is also wildly
8 Scheme 7. The function mechanism of Lewis acid in phenol hydrogenation applied for liquid-phase hydrogenation of phenol because of its
and stabilization of cyclohexanone. Reproduced with permission from ref
9 [3b]. Copyright 2009, American Academy of Arts and Sciences. adjustable pore structure, strong shape-selective catalytic
10 property and acid-base performance.[7b] Hydrotalcite (HT),
11 integrating the physical and chemical properties of Al2O3 and
12 the solution, which suppressed the following hydrogenation MgO, was reported as a good support for phenol hydro-
13 reaction. The lower selectivity of cyclohexanone was owing to genation because the adequate basic sites on HT promote the
14 the rapid isomerization from keto to enol created by the adsorption of phenol.[48] While TiO2, CeO2 and ZrO2 are also
15 interaction between the a-H of cyclohexanone and the OH of good candidates as support in phenol hydrogenation due to
16 basic solution (Figure 6a). But in acidic solution, the catalytic their tunable hydrophilicity and acid-base properties.[47c,49] In
17 addition, non-metal oxides SiO2, as a stable material with
18 tunable porous structure (especially mesopores) and surface
19 groups, is also frequently applied as catalysts support in the
20 liquid-phase hydrogenation of phenol. Sum up, since there are
21 many studies involving the application of oxides in liquid-phase
22 hydrogenation of phenol, here we make a brief summary in
23 terms of the means used to improve the catalytic performance
24 of Metal/Oxides catalysts.
25
26
27 4.2.1. Modification of Catalysts
28
29 Regulation of the active components Based on the theory that
30 low temperature would retard the transfer and aggregation of
31 Pd NPs, Cheng et al. prepared Pd/Al2O3 catalysts containing
32 different particle size of Pd NPs by controlling the reduction
33 temperature.[50] The catalyst with Pd particle size of approx-
34 imately 3 nm (reduced by NaBH4 at 273 K) showed a 98%
35 selectivity of cyclohexanone with exceeding 99% conversion of
36 phenol. The authors attributed the excellent performance of
37 this catalyst to the just right interaction formed between
Figure 6. a. Proposed tautomerism reaction of cyclohexenol and cyclo-
38 hydroxyl group of phenol and hydroxyl group of catalysts as
hexanone in the presence of base. b. Potential energy profile for the
39 reaction of cyclohexenol with acetic acid. Reproduced with permission from well as that between the aromatic ring of phenol and Pd NPs.
40 ref [46]. Copyright 2018, The Royal Society of Chemistry. Resende et al. investigated the impact of particle size of the Pd/
41 ZrO2 catalysts.[51] The result showed that liquid-phase hydro-
42 genation of phenol was a structure-sensitive reaction on Pd/
43 activity may remain the same or increase, which depended on ZrO2. The Pd/ZrO2 with higher Pd dispersion came with the
44 the acid used. When using HCOOH or CH3COOH as solution lower turnover frequencies (TOF). Moreover, with the decreas-
45 media, the carbon sites on the COOH groups were in the state ing of particle size, the activation energies got lower while the
46 of deficient electron and presented the similar nature as Lewis coverage got higher, which suggesting the unfavorable
47 acid sites. The benzene ring of phenol polarized on these sites activation entropy might occur on small Pd particles (1–2 nm).
48 led to an increased catalytic activity. Moreover, the increased Ru was also found to be an effective metal component for
49 selectivity was resulted from the effective bonding of the phenol hydrogenation in liquid phase. The Ru/Al2O3 catalyst
50 intermediate cyclohexenol with acid additives, i. e., the inter- prepared by the traditional hydrogen reduction had the Ru NPs
51 mediate would be rapid isomerized to cyclohexanone through size ranging from 10 to 50 nm and showed a 82% conversion
52 the reaction mechanism of double-hydrogen-transformation of phenol with a 67% selectivity of cyclohexanone under mild
53 according to the DFT calculations. The presence of CH3COOH conditions (80 8C, 20 bar H2, 1 h).[52] Besides the traditional
54 reduced the energy barrier of the transformation of cyclo- reduction methods, Raspolli Galletti et al. took the microwave-
55 hexenol to cyclohexanone from 57.1 kcal mol 1 to 14.5 kcal assisted solvothermal method to reduce Ru/Al2O3. The prepared
56 mol 1 (Figure 6b).[46] catalyst with small particle size (2.23 nm) and narrow size
57 distribution achieved a 87% cyclohexanone selectivity with
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1 phenol conversion exceeding 81%.[53] Recently, our group
2 applied the non-noble metal Co to reduce phenol.[54] Although
3 the cyclohexanol was the main product instand of cyclo-
4 hexanone, this was the first time to apply metal Co for phenol
5 hydrogenation. If the selectivity of cyclohexanone can be
6 adjusted to a satisfactory value, the application market of non-
7 noble metals in the field of cyclohexanone production via
8 hydrogenation of phenol will be expanded in the future.
9 Introduction of the heteroatoms Alloying two active noble-
10 metals was demonstrated effectively to develop highly per-
11 formed oxides-supported catalysts. Resende et al. investigated
12 the alloy effect of Ag on Pd/ZrO2 for phenol hydrogenation. The
13 Ag-Pd/ZrO2 gave a TOF of 9 s 1 while only a TOF of 1 s 1 was
14 achieved in Ag-free Pd/ZrO2. The activation energy of phenol
15 hydrogenation reduced from 81 kJ mol 1 to 57 kJ mol 1 due to
16 electron transfer from Ag to Pd.[51] The similar synergistic effect
17 was also observed in PdRu alloys. The significantly increased Figure 7. Potential energy diagrams of phenol hydrogenation on Pd (111)
18 hydrogenation activity could be explained by three aspects: (i) and K-Pd (111). (a) Direct hydrogenation pathway of adsorbed phenol and
19 the addition of Ru promoted the dispersion of Pd NPs, thereby (b) dissociation and hydrogenation pathway of adsorbed phenol and (c)
relevant structures. Blue line represents reaction route over K-Pd (111); red
20 exposing more active sites to facilitate the reaction rate; (ii) the line represents reaction route over Pd (111). Reproduced with permission
21 electronic effect between Ru and Pd promoted the activation of from ref [57]. Copyright 2017, The Royal Society of Chemistry.
22 hydrogen or phenol; (iii) the addition of Ru changed the
23 adsorption manner of phenol which was beneficial for the
24 generation of cyclohexanone.[55] In addition to the formation of Modification of the supports For phenol hydrogenation in
25 alloys, doping with other metals as co-catalysts can also liquid phase, the Pd/Al2O3 with high surface area of 406 m2 g 1
26 improve the performance of catalysts in liquid phase. The (Pd/Al2O3-CWE) achieved a 100% conversion of phenol with
27 function mechanism of these promoters in liquid-phase reac- 98% selectivity of cyclohexanone. Under same reaction con-
28 tions is similar to that in gas phase. An example was Pd-Ce-B/ ditions, only 60% phenol conversion and 78% cyclohexanone
29 HT catalyst prepared by Liu et al, the introduction of Ce (the selectivity could be obtained over Pd/Al2O3 (commercial Al2O3)
30 article only compared the Ce added or not) enhanced the catalyst, which demonstrated that the high specific surface area
31 phenol conversion from 69.6% to 81.7% and the cyclohexanone was of great benefit to achieve high TOF values.[58] Matos et al.
32 selectivity from 69.2% to 80.3%. Three characteristics were prepared TiO2-C hybrid materials via solvothermal method and
33 declared to be responsible for the good catalytic performance supported Pd on TiO2-C as catalysts to reduce phenol. The
34 of this catalyst. Firstly, doping of B increased the interaction product distribution was related to the functionalization of the
35 between Pd2 + and HT by donating partial electrons to Pd; hybrid support. The main product being cyclohexanone was
36 secondly, doping of Ce favored the highly dispersion of Pd; achieved when using Pd supported on the more polar TiO2-C as
37 thirdly, Ce3 + species acted as Lewis base sites, phenol absorbed catalyst while cyclohexanol dominated the product when the
38 on basic sites of HT in a non-planar form preferred to be hydrophobic TiO2-C was used as support.[59] Unlike Pd-based
39 hydrogenated to cyclohexanone.[56] Wang et al. found that the catalysts, the Pt@TNT (TiO2) catalysts with highly dispersed Pt
40 addition of K or Na improved the conversion of phenol over NPs mainly entrapped inside TNT were successfully prepared by
41 Pd/TiO2 catalyst from 36.8% to 99% without changing the taking the advantage of TNT after hydrophobic modification
42 selectivity of cyclohexanone, then they explored the effect of K- (Figure 8).[60] The hydrophobic modification of TNT increased
43 doping in phenol hydrogenation through DFT calculations for phenol conversion from 46% to 96%. In summary, the hydro-
44 the first time, the results were consistent with previous reports phobic TNT showed its superiority via two terms: (i) the special
45 in the literature.[57] Specifically, compared with the DFT results structure of TNT favored the formation of small Pt particle,
46 in mono Pd system, the long bond length of H O, low activity creating more active sites; (ii) TNT afforded a strong interaction
47 energy and reaction energy of hydrogen dissociation in K-Pd with Pt NPs, endowing the metal particles with a more suitable
48 model illustrated that the doping of K promoted the dissocia- electronic state. Lin and coworkers selectively introduced many
49 tion of phenol to phenoxy and H. Further investigation in the isolated silanol groups distributed on the mesopore surface to
50 Bader charge and charge density of K-Pd model revealed that K decorate SiO2, thereby prepared the functionalized MMT-1
51 enriched the electron density of adjacent Pd atoms. The (sMMT-1 silica). The special structure of sMMT-1 and small Pd
52 potential energy diagram indicated that K significantly en- NPs size (1.1 nm) made the Pd@sMMT-1 catalyst improve the
53 hanced the reaction rate of phenol conversion (blue lines) and phenol conversion from 45% to > 99% accompanying with a
54 had promoting effects in the following three steps: the superior stability (ten catalytic runs) and a high selectivity of
55 dissociation and diffusion of H atom of phenolic hydroxyl, the cyclohexanone (98%).[61] Supporting Pd on MS-C3@MS-NH2, a
56 addition of hydrogen adatom at the ortho position of the kind of mesoporous silica microspheres (MS) with hydrophobic
57 phenoxy and the desorption of cyclohexanone (Figure 7).[57] core and hydrophilic shell (Figure 9), a 98.5% conversion of
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Focus Review
1 surface property of Pd particles was significant changed.[66] The
2 same phenomnon was observed by Wang and coworkers that
3 the acidic nature of the reaction medium and leaching of Pd
4 were responsible for the deactivation of catalysts in high-
5 pressure CO2 (0.3–1.0 MPa) and H2O medium. But they demos-
6 trated that low-pressure CO2 (0.05–0.2 MPa) could enhance the
7 selectivity of cyclohexanone from 84% to 99% with the
8 complete conversion of phenol over Pd/g-Al2O3 catalyst.[67]
9 According to the experimental results and theoretical calcu-
10 lations, the authors put forward that the two interactions,
11 including the Lewis acid-Lewis base interaction between CO2
12 Figure 8. Schematic presentation of the catalyst preparation route: (i) and cyclohexanone carbonyl as well as a weak C H···O
hydrophobic modification; (ii) wet impregnation; (iii) thermal reduction.
13 interaction between CO2 and the hydrogen atoms attached to
Reproduced with permission from ref [60]. Copyright 2014, The Royal
14 Society of Chemistry. the a-carbon atom of cyclohexanone, promoted the departure
15 of cyclohexanone from the Pd surface rapidly and then avoid
16 the excess hydrogenation to produce cyclohexanol. The
17 function mechanism of solvent effect concerning hexane and
18 water was studied in detail by Nelson and coworkers in Pd/
19 CeO2 catalyst system (Figure 10).[68] In hexane solvent, phenol
20
21
22 Figure 9. The synthesis procedure of the Pd/MS-C3@MS-NH2 catalyst.
23 Reproduced with permission from ref [62]. Copyright 2015, The Royal
Society of Chemistry.
24
25
26
27 phenol and 97.1% selectivity of cyclohexanone were gained
28 under mild reaction conditions (1 atm H2, 80 8C, 3 h) when this
29 catalyst used for phenol hydrogenation. While only 38.2% and
30 78.8% of phenol conversion was achieved in Pd/MS-NH2@MS-C3
31 and Pd/MS@MS-NH2 catalysts, respectively. The excellent per-
32 formance could be explained by the synergistic effect between
33 binary organic functional groups of MS-C3@MS-NH2: the C3 (n-
34 propyl group) decreased the diffusion limitation of phenol in
35 aqueous and the -NH2 helped to disperse Pd NPs uniformly
Figure 10. The mechanisms of phenol hydrogenation in water (left) and
36 inside the pores.[62] hexane (right). Reproduced with permission from ref [68]. Copyright 2015,
37 American Chemical Society.
38
39 4.2.2. Adjustment of the Reaction Environments
40 dissociated spontaneously into phenoxy and hydrogen, next,
41 Solvent effect is also studied in oxide-supported catalyst the species bonding with the Ce sites and hydroxyls in CeO2
42 systems. Takagi et al. found that the activity of Ru/Al2O3 for support to form cerium-bound phenoxy and water, respectively.
43 phenol hydrogenation was far better than that of Pt/Al2O3 Chemical binding with the Ce cations decreased the electron
44 when lower alcohols were used as solvents. This phenomenon density of the aromatic ring, which made the aromatic ring be
45 was explained by that the strong interaction between alcohols attacked easily by activated H. With the consumption of -OH
46 and Pt/Al2O3 rather than Ru/Al2O3 prevented Pt/Al2O3 from groups in CeO2, dissociative adsorption of phenol could no
47 effectively adsorbing substrates.[63] In scCO2 systems, Fujita et al. more occurred in later catalytic cycles, which led to the decay
48 reported that Rh/Al2O3 catalysts deactivated in a short period of of activity (Figure 10 right). The catalytic reactivity was lower in
49 time and this deactivation was resulted in the strong water than that in the hexane phase owing to the hydro-
50 adsorption of CO produced from CO2 with the presence of H2 philicity of CeO2. Specifically, the water molecules would easily
51 on Rh/Al2O3.[45] It is a fashion to design green multiphase cover the Ce sites in water phase then inhibited the adsorption
52 reaction systems for organic synthetic reactions.[64] Yet, Yoshida of phenol molecules on support (Figure 10 left).
53 et al. demonstrated that CO2-water multiphase system was not
54 suitable for phenol hydrogenation as the Pd/Al2O3 lost its
55 catalytic activity more rapidly. This is because acidic solution
56 was created when CO2 dissolved in water under high
57 pressures.[65] As a result, plenty of Pd leached out and the
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Focus Review
1 4.3. Metal-Organic Frameworks 4.4. Others
2
3 The regular pores and cavities for metal NPs encapsulation in Polymers ‘‘Soluble’’ nanoparticles restricted on solid surfaces
4 the metal-organic framework materials (MOFs) make them have proven to be more active compared with ‘‘non-soluble’’
5 alternative supports for preparing highly-performed catalysts.[69] nanoparticles.[74] Polymers are often used as stabilizers to make
6 Ertashas et al. used two kinds of metal organic frameworks “soluble” NPs catalysts, providing a new idea to create semi-
7 (MOFs), chromium benzenedicarboxylates MIL-101 and MIL-53, heterogeneous route for selective hydrogenation of phenol to
8 supporting Pd metals to design catalysts used for phenol cyclohexanone. Chen and coworkers combined the preparation
9 hydrogenation.[71] The phenol conversion (85.0%) in Pd/MIL-101 of the water-soluble Pd/A-HPW (A represents ionic liquid-like
10 catalyst was higher than that in Pd/MIL-53 (45.7%) under same copolymer, HPW represents phosphotungstic acid) catalyst with
11 reaction conditions. The main reason why the catalytic perform- the reaction of phenol hydrogenation in a one-pot process.[75]
12 ance of Pd/MIL-101 was better than that of Pd/MIL-53 was that The good catalytic performance (conv. > 99%, sel. > 99) of Pd/
13 the Pd nanoparticles (2.5 nm) in MIL-101 framework were A-HPW catalyst was owing to an ionic cage formed by “A”
14 smaller than in MIL-53 framework (4.7 nm). Thus, more active polymer, which helped immobilize “water-soluble’’ Pd NPs,
15 sites could be exposed. The generation of small Pd NPs was adsorb phenol molecules, stabilize the ionic intermediates and
16 owing to the structural properties of MIL-101 such as meso- desorb cyclohexanone, finally leading to a fast and selective
17 porosity and hydrophilicity, which facilitating the adsorption of hydrogenation of phenol to cyclohexanone. In addition, HPW
18 [PdCl4]2 species into the MIL framework and subsequent could promote the formation of ionic intermediate. The water-
19 reduction inside the pores. Consequently, the metal-p inter- soluble metal NPs with highly dispersion and narrow size
20 action between Pd and MIL-101 was created, and the catalytic distribution can be also obtained and stabilized by poly-(N-
21 activity was improved.[72] Moreover, MIL-101 supported Ru NPs vinyl-2-pyrrolidone) (PVP). More than 99% conversion of phenol
22 was prepared via gas-phase infiltration of Ru-(cod)-(cot) (cod: and 99% selectivity of cyclohexanone were acquired when the
23 1,5-cyclooctadiene; cot:1,3,5-cyclooctatriene) by Ertas and co- Pd/PVP catalyst used for phenol hydrogenation in water
24 workers (Figure 11).[70] In comparison with Ru-based catalysts phase.[76] Macroporous resins, due to their chemical stability
25 and thermal stability, were also used as supports in phenol
26 hydrogenation. For example, the Pd/A-45 (commercial resin
27 Amberlyst-45) received a 89.0% selectivity of cyclohexanone
28 with the completely conversion of phenol during 0.5 h.[77]
29 Zeolites There are only few reports concerning the use of
30 zeolite as support for phenol hydrogenation because of the
31 dominating micropores in zeolite is not conducive to the mass
32 transfer of aromatic compounds. Very recently, Ding and
33 coworkers reported a meso-structured Ru@NaX catalyst com-
34 posed of Ru clusters enclosed in the super cages of X-zeolite
35 and investigated it for the selective hydrogenation of phenol to
36 cyclohexanone for the first time.[78] A phenol conversion of
37 99.9% with a cyclohexanone selectivity of 95.4% was obtained
38 on the Ru@NaX catalyst. The authors attributed the good
39 catalytic performance to the efficient cooperation between the
40 “electron-deficient” Ru clusters and the peripheral X-zeolite
41 skeleton of Ru@NaX.
42 Nitrides Nowadays, nitrides are often reported as supports
43 in the field of heterogeneous catalysis. But for phenol hydro-
44 genation, such support is relatively less used. TiN is a
45 Figure 11. The possible morphology of Ru/MIL-101. Reproduced with biocompatible material with excellent physical and chemical
46 permission from ref [70]. Copyright 2016, Elsevier. stability,[79] when it was taken for one-step hydrogenation of
47 phenol, a high selectivity of cyclohexanone (98%) with exceed-
48 ing 99% conversion of phenol was gained under mild
49 reported previously[73], Ru/MIL-101 prepared by this method conditions (30 8C, 0.2 MPa H2, 12 h).[80] By the way, the authors
50 had a more remarkable selectivity of cyclohexanone (90%) with also investigated the effect of metal particle size in the range of
51 a 90% phenol conversion. The good performance of Ru@MIL- 7–16.5 nm and found that the ketones selectivity increased
52 101 catalyst was due to the existence of Lewis acid sites (Cr3 +) with the increase of Pd particle size. The selectivity reached
53 in MIL-101 framework. The interaction between Lewis acid maximum value at the metal particle around 10 nm.
54 (Cr3 +) on MIL-101 and the Lewis base (C=O group) in cyclo-
55 hexanone inhibited further hydrogenation of cyclohexanone to
56 other byproducts.[3b]
57
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Focus Review
1 4.5. Catalytic Transfer Hydrogenation (CTH)
2
3 Organic molecules, e. g., alcohols, acid and acid salts, can act as
4 hydrogen donors in hydrogenation reactions accompanied
(6)
5 with catalysts through a pathway known as catalytic transfer
6 hydrogenation (CTH). In CTH process, the treatment of high-
7 pressure, flammable hydrogen gas can be avoided and the
8 solubility of hydrogen donors can be enhanced. Furthermore,
9 in comparison to molecular H2, the lower hydrogenating Producing activated H in CTH process requires a relatively
10 capability of most organic hydrogen donors can effective high temperature, thus increases the energy consumption. In
11 control the product selectivity when partially hydrogenated order to improve reactivity thereby to reduce production costs,
12 molecules are targeted.[81] This theory is corking applied for doping with other metals or using auxiliary equipment comes
13 selective hydrogenation of phenol. into a good choice. La-doped Pd/Al2O3 catalysts (Pd/Lax-Al2O3)
14 Xiang et al. explored the catalytic performance of Raney Ni was used in the catalytic system combining the methanol
15 and Pd/Al2O3 catalysts for reducing phenol and proposed a reforming and phenol hydrogenation together.[84] The strong
16 mechanism about hydrogen generation in three different interaction between Pd NPs and La NPs increased The TOF of
17 systems as follows: equations 1–4 represents the generation of Pd/La1-Al2O3 catalyst from 5 h 1 to 16 h 1. The authors consid-
18 hydrogen in situ from the APR of methanol (eqn 1) or ethanol ered that the addition of La promoted the aqueous-phase
19 (eqn 2 and eqn 4), or from the dissociation of H2-gas (eqn 3).[82] reforming of methanol firstly, thus sufficient H was activated.
20 Compared with the excessive adsorbed hydrogen from dissoci- Secondly, the adjunction of La increased the acidity of the
21 ation of H2 gas, the APR of methanol or ethanol produced catalyst, promoting the isomerization of enol to ketone and
22 limited amounts of adsorbed hydrogen. The inhomogeneous inhibiting the further hydrogenation of cyclohexanone to
23 distribution of hydrogen around the adsorbed phenolic species cyclohexanol.[3b] Except for the addition of heteroatom, micro-
24 favored the formation of cyclohexanone but had a negative wave-assistance is also a alternative choice to improve the
25 effect on reaction rate. Zhang et al. compared the catalytic reaction rate. Cheng et al. found that Pd/C used in the CTH
26 performance of different Pd-based catalysts in different con- process of phenol acquired an excellent yield of cyclohexanone
27 ditions.[83] The results showed that, when using molecular H2 as (above 98%) under microwave irradiation with suppling
28 hydrogen source, the activities of catalysts followed the trend: HCOONa aqueous as hydrogen source.[10b] Phenol was com-
29 Pd/MIL-101 > Pd/TiO2-AC > Pd/AC > Pd/C-commercial > Pd/ pletely conversed within 15 minutes under microwave irradi-
30 Al2O3 > Pd/TiO2. In contrast, the activity was changed to the ation, while only 63.6% of phenol conversion was achieved in
31 following order: Pd/AC > Pd/C-commercial > Pd/TiO2-AC > P d/ 300 minutes by conventional heating method. The CTH process
32 MIL-101 > Pd/TiO2 > Pd/Al2O3 when formic acid was employed of phenol with applying HCOONa aqueous as hydrogen donor
33 as hydrogen donor. Based on the fact that both the formic acid included two reactions, i. e., the hydrogen production (eqn 5)
34 decomposition and phenol hydrogenation occurred in CTH and phenol hydrogenation process (eqn 6).
35 system, the two reactions might impact each other and then
36 influence the overall reaction rates. The authors concluded that
37 the optimum catalyst for in situ hydrogenation reactions should 4.6. Electro-catalytic Hydrogenation (ECH)
38 allow all reactants to approach the active sites. The Pd/AC
39 exhibited the highest activity in the CHT process probably Water electrolysis is a superior fashion to produce hydrogen.
40 because of its specific adsorption ability for both phenol and The electro-catalytic hydrogenation (ECH) of phenol,combining
41 formic acid. the electrolysis of water with the reduction of biomass-derived
42 feedstock, can make full use of resource and reduce the cost of
43 (1) hydrogen production.[85] The composition of electrolytes as well
44 as the property of electrode materials, e. g., surface area,
45 conductivity, catalytic activity and long-term stability, decide
(2)
46 the ECH performance of catalysts together.[86]
47 Pt-based catalysts Pt-based catalysts are the most widely
48 (3) used noble-metal catalysts in the field of electrochemistry
49 because of their excellent electro-catalytic performance. Amou-
50 (4) zegar and coworkers investigated the impact of metal electro-
51 chemically active-surface-area and electrode material by using
52 Pt/C electrode for phenol ECH. The results showed that the
53 (5) properties of Pt/C such as metal particle size and electro-
54 chemical surface area had no influence on the hydrogenation
55 activity.[87] However, the electrode material affected the current
56 efficiency, products distribution and the order of reactants. The
57 activity sequence of different electrode materials was as follows:
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Focus Review
1 Pt»Rh > Pd > Ru. Due to limited reserve of Pt, the researchers fixing carboxylate and carboxyl groups of Al2O3 than that of F-
2 focused on the following two aspects to broaden the doped Pd/SnO2.[94]
3 application of Pt-based catalysts: (i) doping with the second
4 metal to reduce the amount of Pt and (ii) modifying the (7)
5 support material of Pt-based catalysts. For example, the
6 addition of Co increased the catalyst selectivity to cyclo-
(8)
7 hexanone by 8.6-fold without affecting phenol conversion.[88]
8 Amouzegar et al. found that the activity of Pt/C electrode was
9 better than Pt/Pt in the process of phenol ECH. According to (9)
10 the literature, depositing Pt (work function 5.4 eV) on a support
11 bearing a lower electron work function, such as carbon
12 material, could improve the electron density of Pt.[89] Thus, they
13 attributed the better activity of Pt/C electrode compared with 5. Conclusions and Perspectives
14 Pt/Pt electrode to the higher electron density of Pt.[87] Based on
15 experiment results, the authors proposed a reaction pathway The production capacity of cyclohexanone will continue at a
16 about the ECH of phenol reacted on Pt electrode shown as large scale in the future because of the ever-increasing demand
17 follows (eqn 7 ~ 9)[90] and they concluded that the rate-deter- for nylon products. The selective hydrogenation of phenol was
18 mining step was the surface reaction between adsorbed species regarded as the most promising strategy to manufacture
19 instead of the step of phenol adsorption. cyclohexanone. Noble-metal catalysts were intensively applied
20 Pd-based catalysts Laplante et al. observed that the for the transformation of phenol to cyclohexanone. The high
21 sequence for ECH activity of phenol among Pd-based catalysts cost of the energy and noble metals motivates us to research
22 was in the following: Pd/BaCO3 < Pd/BaSO4 < Pd/Al2O3. They for the development of efficient technologies and catalysts,
23 proposed that the metal sites activated hydrogen while the which can cut the production cost and simplify the operational
24 oxide sites adsorbed phenol. The rate-determining step in this complexity.
25 case was the transformation of hydrogen from metal surface to Pd-based catalysts, which exhibit outstanding catalytic
26 reactant molecules.[91] However, Song et al. reputed that both activity and cyclohexanone selectivity, were demonstrated to
27 H + and phenol were adsorbed on the metal sites. The ECH of be the best choice for selective hydrogenation of phenol in
28 phenol passed through a Langmuir-Hinshelwood mechanism, both gas and liquid phase. The catalytic performance of the
29 i. e., the adsorbed hydrogen radicals were produced when the noble-metal (Pd, Pt, Ru, Rh) based catalysts was strongly
30 catalyst contacted with the electrode, and then the adsorbed influenced by the supports, promoters, reaction conditions, and
31 phenol molecule reacted with the hydrogen radical generated etc. Although Ni, as a non-noble metal with lower cost, would
32 ketone quickly.[85] Because doping with fluorine can change the be applied for phenol hydrogenation, it generally leads to the
33 non-conductive SnO2 into the conductive form, Tountian et al. hydrogenolysis of phenol to benzene, or even cyclohexane. On
34 chosen SnO2-based powders to study the conductive effect on the whole, recent studies concerning selective hydrogenation
35 the process of phenol ECH.[92] In comparison with non- of phenol concentrate more on the catalytic systems in liquid
36 conductive form, conductive F-doped SnO2 improved the phase. New technologies, such as the CTH and ECH of phenol,
37 electro-hydrogenation rate. The promotion was explained by were developed for the direct hydrogenation of phenol to
38 the fact that conductive powder could polarize all the Pd NPs cyclohexanone with the aim of avoiding the use of explosive H2
39 simultaneously, which was the primary factor governing the gas and making full use of the sustainable H2 from H2O
40 ECH effectiveness. electrolysis, respectively. Even though some prospects can be
41 Electrolytes Electrolyte not only delivers electrons and expected, the catalytic efficiency of these systems is still much
42 provides an acid-base reaction environment but also function- less than satisfactory.
43 alizes the electrode surface. For instance, Cirtiu et al. studied In spite of recent advances, there are still some challenges
44 the effect of electrolyte composition and found that the ECH which can guide the future directions in designing cost-
45 efficiency and product yield decreased with the increasing effective strategies for selective hydrogenation of phenol to
46 amount of methanol in the electrolyte, whereas increased with cyclohexanone, as described below:
47 the addition of aliphatic carboxylic acids.[93] They demostrated Better understanding of adsorption patterns In previous
48 that the additives in electrolytes transferred the catalyst into an works, the viewpoints about adsorption sites and adsorption
49 organically functionalized material, and the modified catalyst patterns of phenol conflict. Some hold that phenol is adsorbed
50 surface could change the adsorption/desorption equilibrium of on the metal site while others deem that phenol adsorbed on
51 the phenol molecules. Tountian et al. confirmed that carboxylic the support. Whether phenol is adsorbed on catalysts by a non-
52 acid in electrolyte solutions could functionalize the support planar form or in a planar manner is also still under debate.
53 surface, thereby modulate the adsorption step of target Since the adsorption behaviors of related molecules decide the
54 molecule.[94] The adsorption of phenol was improved with the requirements for catalysts, better understanding of adsorption
55 increasing hydrophobicity of the functionalized surface. In configuration of the key intermediates by some in situ
56 addition, the ECH performance of Pd/Al2O3 was superior to that techniques and DFT calculations is very necessary.
57 of F-doped Pd/SnO2, this was due to the better capacity in
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Focus Review
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Selective Hydrogenation of Phenol

Article in ChemNanoMat · February 2018

Yutong Gong Shanjun Mao

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