Pore structure control factors of polyamine-bridged polysilsesquioxanes by sol–gel method and their structure-adsorption properties for Au(III)

Figures & data

Scheme 1. Synthesis of monomers.

Figure 1. FTIR spectra of EDA-series samples (1) EDA-BPS, (2) C-EDA, (3) C-EDA/T-1, (4) P-EDA and (5) P-EDA/T-1.

Figure 2. FTIR spectra of DETA-series samples (1) DETA-BPS, (2) C-DETA, (3) C-DETA/T-1, (4) P-DETA and (5) P-DETA/T-1.

Table 1. Parameters of pore structures of DETA-series.

DETA series	BET surface area (m^2 g^−1)	BJH desorption cumulative volume of pores (cm^3 g^−1)	BJH desorption average pore radius (Å)
DETA-BPS	215	0.68	49.27
C-DETA	215	1.01	78.08
C-DETA/T-1	293	1.22	87.22
C-DETA/T-2	464	0.45	22.77
C-DETA/T-4	392	0.26	37.85
C-DETA/T-6	224	0.19	41.44
C-DETA/T-8	165	0.20	82.65
C-DETA/T-10	136	0.26	51.75
C-DETA/T-20	122	0.17	50.15
P-DETA	300	0.98	56.05
P-DETA/T-1	445	0.49	19.87
P-DETA/T-2	425	0.54	21.64
P-DETA/T-4	277	0.82	50.76
P-DETA/T-6	244	0.90	64.44
P-DETA/T-8	199	0.59	55.85
P-DETA/T-10	205	0.72	67.29
P-DETA/T-20	194	0.42	47.25

Table 2. Parameters of pore structures of EDA-series.

EDA series	BET surface area (m^2 g^−1)	BJH desorption cumulative volume of pores (cm^3 g^−1)	BJH desorption average pore radius (Å)
EDA-BPS	7	0.05	208.14
C-EDA	9	0.03	83.58
C-EDA/T-1	597	0.33	15.13
C-EDA/T-2	419	0.23	18.90
C-EDA/T-4	354	0.38	34.07
C-EDA/T-6	352	0.45	47.88
C-EDA/T-8	149	0.26	65.69
C-EDA/T-10	144	0.32	71.61
C-EDA/T-20	101	0.25	91.64
P-EDA	110	0.55	82.96
P-EDA/T-1	498	0.78	25.08
P-EDA/T-2	415	0.78	29.56
P-EDA/T-4	356	0.57	29.18
P-EDA/T-6	332	0.74	41.91
P-EDA/T-8	292	0.75	35.10
P-EDA/T-10	290	0.74	48.66
P-EDA/T-20	249	0.72	51.96

Scheme 2. Schematic diagram of interaction of TEOS with bridged monomer.

Figure 3. Nitrogen adsorption–desorption isotherms of representative samples of DETA and EDA series.

Figure 4. BJH desorption pore size distributions of representative samples of DETA and EDA series.

Figure 5. Representative FESEM images of DETA-BPS, C-DETA, C-DETA/T-2, C-DETA/T-20, P-DETA, P-DETA/T-1 and P-DETA/T-20.

Figure 6. Representative TEM images of DETA-BPS, C-DETA, C-DETA/T-2, C-DETA/T-20, P-DETA, P-DETA/T-1 and P-DETA/T-20.

Figure 7. The adsorption capacities of BPS materials of DETA-series and EDA-series for Au(III).

Table 3. Elemental composition of the DETA-series materials.

DETA series	C%	H%	N%	N (mmol/g)	Au/N
DETA-BPS	26.57	6.62	9.54	6.81	0.66
C-DETA	35.02	6.15	5.93	4.24	1.27
C-DETA/T-1	20.64	4.74	3.12	2.51	1.62
C-DETA/T-2	17.64	3.74	2.82	2.01	1.64
C-DETA/T-4	9.75	2.51	1.33	0.95	0.88
C-DETA/T-6	8.89	2.21	1.01	0.72	0.81
C-DETA/T-8	2.01	0.58	0.92	0.65	0.20
C-DETA/T-10	15.38	3.84	0.85	0.59	0.03
C-DETA/T-20	5.62	1.97	0.56	0.40	0.38
P-DETA	32.91	5.82	5.25	3.75	1.12
P-DETA/T-1	14.70	3.14	2.02	1.44	1.29
P-DETA/T-2	10.99	2.43	1.50	1.07	1.13
P-DETA/T-4	9.75	2.39	2.03	1.45	0.53
P-DETA/T-6	7.86	2.00	1.59	1.14	0.53
P-DETA/T-8	7.22	1.94	1.46	1.04	1.01
P-DETA/T-10	6.66	1.91	1.26	0.90	0.59
P-DETA/T-20	0.14	1.17	0.79	0.56	0.02

Table 4. Elemental composition of the EDA-series materials.

EDA series	C%	H%	N%	N (mmol/g)	Au/N
EDA-BPS	25.87	5.68	6.55	4.68	0.32
C-EDA	30.34	0.80	5.26	3.76	0.39
C-EDA/T-1	45.77	8.56	4.25	3.04	0.36
C-EDA/T-2	13.14	2.90	1.14	0.81	0.96
C-EDA/T-4	8.94	2.35	0.82	0.59	1.87
C-EDA/T-6	6.65	0.56	0.66	0.49	0.69
C-EDA/T-8	22.87	5.23	0.60	0.42	0.98
C-EDA/T-10	6.84	1.75	0.58	0.41	0.55
C-EDA/T-20	8.40	1.99	0.53	0.38	0.03
P-EDA	27.95	6.44	7.00	5.00	0.30
P-EDA/T-1	24.88	4.32	2.74	1.96	0.50
P-EDA/T-2	13.51	2.92	1.94	1.39	0.46
P-EDA/T-4	0.05	0.91	0.50	0.36	1.57
P-EDA/T-6	15.91	3.25	0.65	0.42	1.39
P-EDA/T-8	5.90	1.49	0.54	0.39	1.59
P-EDA/T-10	6.62	1.71	0.76	0.54	0.02
P-EDA/T-20	6.09	1.85	0.70	0.50	0.02

Table 5. XPS binding energies (eV) in DETA-BPS, C-DETA and P-DETA samples before and after Au(III) adsorption, and XPS binding energies of Au(III), Au(I) and Au(0) in references.

	N1s	O1s	Au 4f
DETA-BPS	398.67, 401.02	531.67
DETA-BPS-Au	398.89, 401.20	531.76	84.08, 85.99, 87.73
C-DETA	398.86, 401.33	531.83
C-DETA-Au	399.67, 401.46	532.07	84.70, 87.03, 88.31, 91.02
P-DETA	398.89, 401.37	531.93
P-DETA-Au	399.59, 401.37	532.02	84.51, 85.63, 87.01, 88.19, 89.35
Au(III) (in [AuCl4]^−) [20]			87.50, 91.20
Au(I) (in AuCl) [20]			84.35, 88.91
Au(0) (in silicate minerals) [21]			84.00, 87.60

Table 6. Saturated adsorption capacities for Au(III) of C-DETA prepared in the present work in comparison with those of recently reported adsorbents.

Adsorbents	Saturated adsorption capacities for Au(III) (mmol g^−1)	References
Polystyrene-supported 3-amino-1,2-propanediol	1.17	[18]
Graphene oxide	0.55	[22]
Silica hybrid quaternary ammonium salts	0.32	[23]
Silica functionalized by an amino phosphonic acid	1.19	[24]
Silica modified with N,N-(octane-1,8-diylidene)di(2-hydroxyl-3,5-dimethylaniline)	0.93	[25]
Silica modified with 6-((2-(2-hydroxy-1-naphthoyl)hydrazono)methyl)benzoic acid	1.03	[26]
Silica functionalized with 3-(2-aminoethylamino)propyl	0.50	[27]
Bayberry tannin on mesoporous silica	3.25	[28]
Polyamidoamine-grafted silica gel	2.45	[29]
Ordered mesoporous silica monoliths	0.90	[30]
PDMC-SNP	0.64	[31]
Alkoxycarbonyl thiourea resin	4.65	[32]
Triazine-triethylenetetramine polymers	5.07	[33]
Modified thiol cotton fiber	0.35	[34]
Polystyrene-supported open-chain crown ether	3.20	[35]
C-DETA	5.40	This work

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