Palladium nanoparticles supported on amine-functionalized glass fiber mat for fixed-bed reactors on the effective removal of hexavalent chromium by catalytic reduction

doi:10.1016/j.jmst.2017.05.013

Abstract

Abstract:

Palladium nanoparticles were deposited on the amine-grafted glass fiber mat (GFM-NH₂) catalyst support by a conventional impregnation process followed by the borohydride reduction in aqueous solution at room temperature to create the designed Pd/GFM-NH₂ catalyst. By the use of large size glass fiber mat without nano/mesopores as the catalyst support, the internal mass transfer limitations due to the existence of nano/mesopores on the catalyst support were eliminated and the Pd/GFM-NH₂ catalyst could be easily separated from treated water due to the large size of the catalyst support. Batch experiments demonstrate its good catalytic reduction performance of Cr(VI) with formic acid as the reducing agent. It also demonstrated an efficient Cr(VI) removal and stability in a lab-prepared, packed fixed-bed tube reactor for the continuous treatment of Cr(VI)-containing water. Thus, it has a good potential for the catalytic reduction of Cr(VI) in the water treatment practice.

Key words: Palladium nanoparticle, Amine-functionalized glass fiber mat, Fixed-bed reactor, Hexavalent chromium, Catalytic reduction

Yu Gao, Wuzhu Sun, Weiyi Yang, Qi Li. Palladium nanoparticles supported on amine-functionalized glass fiber mat for fixed-bed reactors on the effective removal of hexavalent chromium by catalytic reduction[J]. J. Mater. Sci. Technol., 2018, 34(6): 961-968.

Figures/Tables 12

Fig. 1. FTIR spectra of GFM, GFM-NH2, and Pd/GFM-NH2 catalysts with various Pd contents.

Fig. 2. (a) XRD patterns of GFM-NH2 and Pd/GFM-NH2 catalysts prepared with H2PdCl4 solutions with various concentrations, (b) representative XPS survey spectrum of the 2.65Pd/GFM-NH2 sample. Inset in Fig. 2(b) shows the high-resolution XPS scan over Pd 3d peaks of the 2.65Pd/GFM-NH2 sample.

Fig. 3. (a) Optical images of the representative 2.65Pd/GFM-NH2 catalyst by itself, in the stirring paddle for the batch reactor, and in the fixed bed reactor, (b) representative SEM image of the 2.65Pd/GFM-NH2 sample, (c) the representative SEM image and EDS analysis result of Pd in related regions of the 2.65Pd/GFM-NH2 sample.

Fig. 4. Representative TEM image of (a) the 0.96Pd/GFM-NH2 catalyst and (b) the 2.65Pd/GFM-NH2 catalyst (the insets in them show the particle size distributions of Pd nanoparticles and the HRTEM image of the Pd nanoparticle with red circle).

Fig. 5. (a) BET measurement curves of the 2.65Pd/GFM-NH2 sample by the N2 adsorption/desorption isotherm measurement; the magnified SEM images obtained on the SiO2 fiber (b) and PVA film (c) of the 2.65Pd/GFM-NH2 sample.

Fig. 6. (a) Light absorbance spectra of Cr(VI) solutions treated by different experimental setups, (b) optical images of the initial Cr(VI) solution, Cr(VI) solution after the catalytic reduction treatment, and the treated Cr(VI) solution with the addition of excessive NaOH.

Fig. 7. Remaining Cr(VI) concentration in treated Cr(VI) solutions with different initial FA concentrations (a), different initial SF concentrations (b) and different Pd contents (c) at different treatment time.

Table 1 Kinetics parameters obtained in fitting the experimental data in Fig. 7(a).

	0 M FA	0.22 M FA	0.44 M FA	0.66 M FA
K_obs (mM min^-1)	0.0001	0.0258	0.1113	0.0592
R²	0.999	0.976	0.965	0.999

Table 2 Kinetics parameters obtained in fitting the experimental data in Fig. 7(b).

	0 M SF	0.22 M SF	0.44 M SF	0.66 M SF
K_obs (mM min^-1)	0.0170	0.0756	0.1113	0.0543
R²	0.996	0.998	0.965	0.991

Table 3 Kinetics parameters obtained in fitting the experimental data in Fig. 7(c).

	0.49Pd	0.96Pd	1.84Pd	2.65Pd
K_obs (mM min^-1)	0.0733	0.0983	0.1030	0.1113
R²	0.978	0.998	0.962	0.965

Table 4 Comparison of the catalytic Cr(VI) reduction activities of various Pd catalysts, which can be used in fixed-bed reactors.

Catalyst	Condition	Conversion time(min)	Initial reaction rate^a (mmol_Cr/g_Pdh)	TOF^b (h^-1)	referances
0.96Pd/GFM-NH₂	2 mM Cr₂O₇^2-, 0.44 M FA, 0.44 M FA, 9.60 mg_Pd/L_aq, 20 °C	20	1250	133	This work
9.1Pd/biofilm	1 mM CrO₄^2-, 25 mM FA, pH=2, 709 mg_Pd/L_aq, 20 °C	183	1.13	0.049	[38]
5.5Pd/Al₂O₃ film^c	0.37 mM Cr₂O₇^2-, 0.82 M FA, 4.95 mg_Pd/L_aq, 50 °C	40	517	24	[39]
13.1Pd/PEI/PVA nanofibers	1.11 mM Cr₂O₇^2-, 0.85 M FA,7.44 mg_Pd/L_aq, 50 °C	12	1920	158	[40]

Fig. 8. (a) Cr(VI) concentration in the effluent at different time in the fixed-bed reactor with the optimal 0.96Pd/GFM-NH2 catalyst; (b) FTIR spectra of the 0.96Pd/GFM-NH2 catalysts before and after use.

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