Modified cellulose with tunable surface hydrophilicity/hydrophobicity as a novel catalyst support for selective reduction of nitrobenzene

Article abstract of DOI:10.1016/j.catcom.2020.105949

Cellulose with tailorable hydrophilicity/hydrophobicity were synthesized by grafting F-containing groups and utilized as supports for palladium nanoparticles. The obtained catalysts were applied in the synthesis of N-phenylhydroxylamine from controllable reduction of nitrobenzene. Unexpectedly high conversion and selectivity could be achieved with 25 ppm Pd catalyst at room temperature in water. The precise modification of the catalyst surface is crucial to realize this targeted transformation. Further investigation indicated that modified cellulose with a more hydrophobic surface would favour the adsorption of nitrobenzene over N-phenylhydroxylamine thus prevent full hydrogenation to aniline.

Full text of DOI:10.1016/j.catcom.2020.105949

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Modified cellulose with tunable surface hydrophilicity/
hydrophobicity as a novel catalyst support for selective reduction
of nitrobenzene
Dan-dan Li, Guo-ping Lu, Chun Cai
PII:
S1566-7367(20)30025-X
DOI:
https://doi.org/10.1016/j.catcom.2020.105949
CATCOM 105949
Reference:
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
17 December 2019
23 January 2020
29 January 2020
Please cite this article as: D.-d. Li, G.-p. Lu and C. Cai, Modified cellulose with tunable
surface hydrophilicity/hydrophobicity as a novel catalyst support for selective reduction
of nitrobenzene, Catalysis Communications (2020), https://doi.org/10.1016/
j.catcom.2020.105949
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Modified cellulose with tunable surface hydrophilicity/hydrophobicity as a novel
catalyst support for selective reduction of nitrobenzene
Dan-dan Li[a], Guo-ping Lu[a] and Chun Cai[a][b]
[a] Chemical Engineering College, Nanjing University of Science and Technology, 200 Xiao Ling W ei, Nanjing 210094, Jiangsu, People’s Republic of China
[b] Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, People’s Republic of
China.
A RT ICLE INFO
AB S TR AC T
Article history:
Received
Cellulose with tailorable hydrophilicity/hydrophobicity were synthesized by grafting F-
containing groups and utilized as supports for palladium nanoparticles. The obtained catalysts
were applied in the synthesis of N-phenylhydroxylamine from controllable reduction of
nitrobenzene. Unexpectedly high conversion and selectivity could be achieved with 25 ppm Pd
catalyst at room temperature in water. T he precise modification of the catalyst surface is crucial
to realize this targeted transformation. Further investigation indicated that modified cellulose
with a more hydrophobic surface would favour the adsorption of nitrobenzene over N-
phenylhydroxylamine thus prevent full hydrogenation to aniline.
Received in revised form
Accepted
Available online
Keywords:
hydrophilicity/hydrophobicity
Palladium nanoparticles
Cellulose
Reduction
Catalysis
1. Introduction
N-arylhydroxylamines represent an important class of chemical intermediates[1]. Selective reduction of nitroarenes is considered to
be the most important and feasible strategy to produce N-arylhydroxylamines. At present, N-arylhydroxylamines are mainly produced
by reduction of nitrobenzene with stoichiometric zinc as reductant [2, 3], which is an environmentally unfriendly strategy. Compared
with the traditional reduction procedure, metal-catalytic reduction is regarded as a greener methodology to produce N-
arylhydroxylamines. However, catalytic reduction of nitroarenes is a consecutive process, and usually continues until anilines were
formed [4-6]. Therefore, improving the selectivity of N-arylhydroxylamines has long been a significant challenge. Recently, several
rhodiumand platinumcatalysts have been reported to be efficient catalysts forselective reduction of nitrobenzene[7-11]. However, few
reports about Pd-catalyzed selective reduction of nitroarenes to N-arylhydroxylamines was reported [12], because the high activity of
Pd catalysts might lead to over-reduction[13-15]. Inspired by previous works, we turned to study approaches to enhance the selectivity
of Pd catalysts.
Recently, tuning the catalytic activity and selectivity by surface modification has generated a tremendous level of attention [16-18].
Most surface modification, especially hydrophilicity/hydrophobicity regulation, can strongly affect the adsorption/desorption of
reactants and the reaction intermediates on the catalyst surface and thus improve the activity and/or selectivity of the product[19, 20].
For example, a hydrophobic surface can enrich a hydrophobic reactant around active sites in aqueous phase and then accelerate the
corresponding reactions[21, 22]. In the case of synthesis of N-phenylhydroxylamine (PHA), hydrophobic surface of catalysts will
enrich hydrophobic nitrobenzene and repel the adsorption of hydrophilic PHA, and thus prevent further reduction of PHA. In this study,
naturally renewable cellulose was chosen as the catalyst support for the presence of a large number of modifiable hydroxyl groups[23-
25]. Cellulose is a super-hydrophilic polymer that can be evenly dispersed in water. On the other hand, fluorine possess unique
properties,such as high electronegativity and relatively small size. Thus fluorine usually has unexpected influence on the properties of a
given compound orsupport [26-28]. Furthermore, the F-containing groups modified surface was reported to be highly hydrophobic[29],
which was supposed to make the modified materials more suitable for organic reactions in aqueous media. Modification of cellulose by
attaching highly hydrophobic F-containing groups would be a great choice for surface hydrophilicity/hydrophobicity regulation of
cellulose.
Herein, we reported the synthesis of perfluoroalkyl-modified cellulose supported ultra-small Pd NPs via a solid state method. The
obtained Pd catalyst exhibited excellent activity and selectivity in the reduction of nitrobenzene to PHA under mild conditions. The Pd
catalyst amount used in this reaction is as low as 25 ppm. The small size of Pd NPs and the influence of F-containing groups were
supposedto be the main reasonsforthe high activityand selectivity ofPd catalysts.
2. Experimental Section
2.1. Cellulose modification
 Corresponding author. Tel.: +86-25-84315514; fax: +86-25-84315030; e-mail: c.cai@njust.edu.cn

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2
In a typical procedure, α-cellulose (1 g) was dispersed in dry DMF (10 mL). Then the mixture was sonicated for 30 min to obtain
equally distributed cellulose suspension. The suspension was cooled to 0 °C and NaH (700 mg) was added in two portions. After
stirring for 30 min, 1H, 1H, 2H, 2H-perfluoroalkyl iodide (1g) was slowly added and the reaction mixture was warmed to room
temperature. After stirring overnight, the reaction mixture was filtrated. The solid was washed with DMF, deionized water and
ethanolbefore dried at 60°C for 10 h. The final product was obtainedas yellowish solid and denotedas CnF2n+1-Cell.
2.2. Catalysts preparation.
A 300 mg amount of CnF2n+1-Cell and 10 μL 5 mg/mL PdCl2 solution was mixed and milled manually for 20 min in an agate mortar.
The samples were kept for 24 h to achieve adsorption of Pd ions on the surface of Cellulose. Thereafter, 60 mg of sodiumformate was
added to the powder mixture and ground for 30 min and kept for another 24 h. The as-prepared samples were washed repeatedly with
distilled water and ethanol to remove unreacted PdCl2 and sodium formate. The obtained samples (Pd@ CnF2n+1-Cell) were dried in in
vacuumoven at 25°C for 12 h.
2.3. Hydrogenation ofnitrobenzene.
Typically, 0.2 mmol nitrobenzene, sodiumborohydride, catalyst and 3mL distilled water was added into a 15mL tube, then the tube
was sealed with a polytetrafluoroethylene plug. The mixture was stirred at 30oC and monitored by TLC. Upon completion of the
reaction,catalysts were separated by centrifugation.The reaction mixture was analyzed by HPLC.
2.4. Adsorptionexperiments.
The adsorption experiments were carried out at roomtemperature. Catalysts (3mg) was dispersed in 1 mL water solutions containing
various concentrations of nitrobenzene or PHA. After vigorous stir for 10 min, the catalyst were separated by centrifugation. The
remained amounts of nitrobenzene or PHA in the supernatants were analyzed by HPLC. The amounts of nitrobenzene or PHA adsorbed
on the surface of catalysts were determined by the change of concentrations before and after adsorption. For the HPLC measurement,1-
hexanolwas introduced asan internalstandardin the methanolsolution,
2.5. Characterization.
TEM images were taken using a PHILIPS Tecnai 12 microscope operating at 120kv. Energy Dispersive X-ray Spectroscopic
analysis (EDS) was performed with a JEM-2010(HR) transmission electron microscope at an acceleration voltage of 200kV. High
Resolution Transmission electron microscopy (HRTEM) was performed on Philips-FEI Tecnai G2 F20 operating at 300kv. X-ray
photoelectron spectroscopy (XPS) were performed on a ESCALAB 250Xi spectrometer, using a Al Kα X-ray source (1350 eV of
photons) and calibrated by setting the C 1s peak to 284.60 eV. Inductively coupled plasma mass spectrometry (ICP-MS) was analyzed
on Optima 7300 DV.
3. Results anddiscussion
3.1. Characterization ofPd/Cell and Pd/C6F13-Cell
The morphologies and microstructures of the obtained catalysts were characterized by SEM and TEM. The SEM images of Pd/Cell
and Pd/C6F13-Cell in Fig. S1 indicate that C6F13-Cell has a much rougher surface compared with pristine cellulose, which can benefit the
adsorption of Pd ions onto support surface. Pd NPs were unable to see because of their tiny size and low loading on both Cell and
C6F13-Cell. Distribution of Pd NPs on C6F13-Cell surface was investigated by TEM (Fig. 1a and S2). Fig. 1a revealed that Pd NPs in
round shape are uniformly dispersed on C6F13-Cell and size of the NPs mainly distribute among 1.0 and 2.5nm. The uniformdispersion
of Pd NPs was also exhibited in HAADF-STEM images (Fig. S3). It was apparent that Pd NPs in Pd/C6F13-Cell are much smaller
compared to Pd NPs supported on pristine cellulose (Fig. S4). The comparison suggests that fluorinated compounds may benefit the
stabilization of Pd[30, 31], resulting in smaller NPs. The ultrafine NPs can provide more contact opportunities between the reactants
and the active sites, which was the prerequisite for high catalytic activity. Moreover, the image showed no aggregation of Pd NPs to a
large degree (Fig. S2). HRTEM analysis was carried out to verify the formation of Pd NPs (Fig. 1b), as shown in Fig. 1b, the NPs have
clear crystalline fringe patterns and the lattice distance is measured to be 0.23nm, which coulpd be assigned to the d-spacing of the
(111) plane of Pd0. Furthermore, the element mappings (Fig. S5) reveals that F and Pd atoms are uniformly distributed on the surface of
cellulose. Therefore, we can confirmthat the cellulose supported small Pd NPs catalyst with F-containing groups modified the cellulose
surface,was successfully preparedvia the solid-state pathway.
Fig. 1 (a) TEM and (b) HRTEM images of Pd/C6F13-Cell.
Since the modification of cellulose was confirmed to be successful, the effect of F-containing groups on the
hydrophilicity/hydrophobicity was further investigated. The air–water contact angles on the surface of Cell and C6F13-Cell are 18.05o
and 42.68o (Fig.S6a and S6c). In order to regulate the hydrophilicity/hydrophobicity of cellulose surface, cellulose with different

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surface modifiers were also synthesized. As displayed in Fig.S6 perflourine-alkyl with a shorter length led to a lower air–water contact
angle, 30.89o, while longer perflourine-alkyl led to a higher air–water contact angle, 65.70o (Fig.S6b and S6d). Although grafting F-
containing modifiers makes cellulose surface more hydrophobic, modified cellulose still retained great hydrophilic nature, which make
themprefect supports forreactionsin aqueous phase.
XPS measurements were carried out to further investigate the chemical state of surface atoms in Pd/C6F13-Cell (Fig. 2, S7, S8 and
S9) and Pd/Cell (Fig. 2, S10 and S11). In Fig. S7, the survey clearly exhibits the presence of C, O, F and Pd elements in Pd/C6F13-Cell
surface. However, due to the low content of Pd of 0.01% (Table S2), XPS peaks of Pd 3d could not be identified. So the XPS
characterization of Pd was carried out with 0.5% Pd/C6F13-Cell. The Pd 3d region spectrum reveals that Pd0 and Pd2+ coexist on the
surface of the catalyst. According to the calculation from the XPS Pd 3d peaks, the Pd element mainly exists in metallic state (Table
S1). A small amount of Pd was oxidized under ambient conditions, resulting in Pd2+ species. There is an obvious shift of binding energy
of Pd0 3d5/2 compared with Pd0 supported on cellulose without F-containing modifiers, indicating the electron transfer between F and Pd
NPs. The distribution of Pd species calculated from the XPS Pd 3d peaks, shows that the contents of the Pd0 in Pd/C6F13-Cell and
Pd/Cell were 79% and 58%, respectively (Table S1), the slight difference might because of the storage environment and
characterization process.
Fig. 2 Pd 3d XPS spectrum of Pd/C6F13-Cell and Pd/Cell.
3.2. Catalytic performance ofthe catalysts
In the selective reduction of nitrobenzene to PHA, water was chosen as a green solvent considering its environmentally friendly
nature. The catalytic performances of the catalysts with different perfluoroalkyl groups were displayed in Table 1, entries 1-5. Pd/Cell
gave lowest nitrobenzene conversion and moderate selectivity to PHA (entry 1). As for the F-containing catalysts, the results clearly
demonstrate that longer perfluoro-carbon chain gave higher catalytic activity. Pd/C8F17-Cell showed highest activity with almost 100%
conversion of nitrobenzene but only 83% PHA in 1 h (entry 4), which might because the higher activity resulted in accumulation of
nitrosobenzene intermediate , then nitrosobenzene and in situ converted PHA readily condenses to azoxybenzene[32]. Shorter time
resulted in higher selectivity but lower conversion of nitrobenzene (entry 5). Pd/C4F9-Cell gave only 70% conversion of nitrobenzene
while Pd/C6F13-Cell gave almost full conversion and 95% selectivity to PHA (entries 2 and 3). It is obvious that Pd/C6F13-Cell has the
best performance in the reduction of nitrobenzene with excellent conversion and selectivity. Moreover, the results clearly indicate that
modification of Pd/Cell with perfluoroalkylgroupscan not only improve the activity butalso the selectivity ofthe catalyst.
With the most suitable catalyst in hand, the reaction conditions was optimized. First, the effect of catalyst amount was examined.
Excellent conversion and selectivity can be achieved with 25 ppm Pd/C6F13-Cell (entry 6). Little over-reduction occurred over 75 ppm
catalyst, (entry 7). However, when the reaction temperature was increased to 50 oC, aniline was determined to be the main product with
a selectivity of 64% and 12% azoxybenzene was also detected (entry 8), which is expected because higher temperature usually cause
over-reduction of nitrobenzene. At last, the amount of reducing agent was optimized. Nitrobenzene can only be partly converted with
o
2.0 equivalent or 1.0 equivalent NaBH4 (entries 9-10) and can hardly be reduced with 0.5 equivalent NaBH4 (entry 11) at 30 C.
Therefore, the optimized reaction conditions forselective reduction of nitrobenzene to PHA was 30 oC with 3.0 equivalent NaBH4 over
25 ppmPd/C6F13-Cell.
The process of reduction reaction catalysed by Pd/C6F13-Cell was further studied by tracing the concentrations of reactant and
products along with the reaction time (Fig. 3). The initial reaction rate was fast in terms of nitrobenzene conversion and formation of
PHA. In the first hour, little aniline and azoxybenzene was detected. After complete consumption of nitrobenzene, PHA, formed up to
95%, was obtained as the main product of the first period. In the second period, azoxybenzene and aniline were formed in a relatively
slowrate along with the consumption ofPHA.Afteranother2h,aniline was the main final product.
Table 1
Evaluation of the reaction parameters on the selective reducion of nitrobenzene to PHA a.

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4
Tetrahedron
Entry
Cat. (ppm)
[H]
Con.(%) [b]
Sel.(%)[b]
1
2
3
Pd/Cell(50)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(3.0)
NaBH4(2.0)
NaBH4(1.0)
NaBH4(0.5)
30
30
30
30
30
30
30
50
30
30
30
43
70
98
>99
86
75
92
Pd/C4F9-Cell(50)
Pd/C6F13-Cell(50)
Pd/C8F17-Cell(50)
Pd/C8F17-Cell(50)
Pd/C6F13-Cell(25)
Pd/C6F13-Cell(75)
Pd/C6F13-Cell(50)
Pd/C6F13-Cell(50)
Pd/C6F13-Cell(50)
Pd/C6F13-Cell(50)
95(89c)
83
4
5d
6
91
96
93
24
>99
>99
-
98
7
8
9
10
>99
>99
49
13
<1
11
a
Reaction condition: the reaction was carried out under air atmosphere in 3 mL water containing 0.2 mmol of nitrobene.
Catalyst amount based on Pd. b Determined by HPLC. c Isolated yield. d Reaction time was 30min.
Fig. 3 Reaction profile fornitrobenzene reduction. Reactioncondition: the reactionwas carriedout in 3 mLwater containing0.2mmol ofnitrobenzeneat 30°C.
Pdamount is 25ppm.
In order to investigate the role of surface property in the high activity and selectivity, adsorption behaviour of nitrobenzene and PHA
on Pd/Cell and Pd/C6F13-Cell was studied (Fig. 4). The adsorption curve of nitrobenzene apparently shows more nitrobenzene was
adsorbed by Pd/C6F13-Cell (508 μmol/g catalyst) at the same nitrobenzene concentration compared with nitrobenzene was adsorbed by
Pd/ Cell (315 μmol/g catalyst). The adsorption capacity of Pd/C6F13-Cell for PHA was 53 μmol/g catalyst, which was much lower than
the adsorption capacity of Pd/Cell of 226 μmol/g catalyst. The enrichment of reactants around the catalyst will accelerate the reduction
reaction. After PHA was formed, PHA could rapidly desorb form Pd/C6F13-Cell catalyst. This explains the slow rate of the conversion
of PHA to aniline and azoxybenzene over Pd/C6F13-Cell. It can be inferred that modified cellulose could accelerate the conversion of
nitrobenzene but prevent the further reduction of PHA. Therefore, the surface property played a critical role in the selective reduction of
nitrobenzene andwas the decisivefactorthat affect the finalproduct.
250
(b)
(a)
Pd/Cell
Pd/C4F9-Cell
Pd/Cell
Pd/C6F13-Cell
500
200
150
100
50
400
300
200
100
0
100
200
300
400
500
100
200
400
Concentration of3n0i0trobenzene5(0p0pm)
Concentration of PHA (ppm)
Fig. 4 Adsorption of (a) nitrobenzene and (b) PHA on Pd/Cell and Pd/C6F17-Cell
3.3. RecyclabilityofPd/C6F13-Cell
Finally, reusability of the Pd/C6F13-Cell catalyst was also investigated. Catalysts were separated by centrifugation, washed with
deionized water and directly used in next cycle without further drying. As shown in Fig. S14, the catalyst delivered excellent catalytic
activity and selectivity for at least five cycles. After 5 runs, the conversion was decreased to 80% while the selectivity remained up to
96%, indicating the activity of the Pd/C6F13-Cell catalyst decreased with the reuse number but the selectivity was not affected by the
recycle procedure. ICP characterization of recycled Pd/C6F13-Cell catalyst shows slight leaching of Pd (Table S2). Increase in the size of
Pd NPs and slight agglomeration were observed in the TEM images of the recycled catalyst (Figure S15). Moreover, the reused catalyst
was characterized by XPS, oxidation of Pd was also observed(Figure S17 and Table S1). The characterization and the recycling results
indicated that thePd contentand particle size and valence state ofPd has no influence on thecatalystselectivity.

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4. Conclusions
In summary, perfluorohexyl modified cellulose was successfully synthesized and utilized as support for Pd NPs. The obtained
catalyst showed unexpected high activity and selectivity to the selective reduction of nitrobenzene to PHA. The excellent catalytic
performance ofPd/C6F13-Cell is mainly attributed to the following reasons:
(i)
F-containing modifiers would alter the adsorption behaviour of N-containing aromatics on catalysts. Modified cellulose has
strong absorbability fornitrobenzene but weakabsorbability forPHA,which could improve not only the activity but also theselectivity.
(ii)
The ultrafine size of Pd NPs ensures wellcontactbetween theactive sitesand the reactants.
(iii)
Presence of F-containing groups results in the enrichment of electrons on the metal surfaces for Pd/C6F13-Cell and lead to
higherPd0 content
The outstanding catalytic performance Pd/C6F13-Cell in our work indicates regulated hydrophilicity/hydrophobicity play an
important role in selectivity reduction, and we believe that the superior modified cellulose may have promising potential for the organic
synthesis.
Acknowledgments
We gratefully acknowledge Chinese Postdoctoral Science Foundation (2015M571761, 2016T90465) for financial support. This work
was a project fundedby the Priority Academic Program.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the workreported in this paper.
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Credit Author Statement
Author contributions
Dan-dan Li: Conceptualization, Methodology, Software, Investigation, Formal analysis, Data curation,
Validation, Writing-Original Draft,:
Guo-ping Lu: Writing-Reviewing & Editing.
Chun Cai: Writing-Reviewing & Editing, Supervision

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Declaration of Interest Statement
The authors declare thattheyhaveno known competing financialinterestsorpersonalrelationshipsthatcould have appeared to
influence the workreported in this paper

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Highlights:
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Cellulose with tunable surface hydrophilicity/hydrophobicity was synthesized.
Pd nanoparticles on modified cellulose was prepared.
Superior catalytic performance of reduction of nitrobenzene was achieved.
Hydrophilicity/hydrophobicity of cellulose surface played a crucial role in the reaction.