In Situ Synthesis of Nickel-Aluminum Hydrotalcite and Its Adsorption Performance on Cr(VI)

doi:10.16553/j.cnki.issn1000-985x.2025.0102

Abstract

Abstract: The hierarchical Ni-Al layered double hydroxides （NiAlNO₃-LDH@NF） were fabricated in situ via a hydrothermal synthesis method using nickel foam （NF） as the carrier and NH₄NO₃ as the precipitant. The crystal structure， morphologies and adsorption performance of NiAlNO₃-LDH@NF as a function of crystallization time and temperature， Al（NO₃）₃ concentration， solid-liquid ratio and Al³⁺/NH₄NO₃ molar ratio were investigated by XRD， SEM characterization and macroscopic adsorption experiments. The adsorption properties， mechanism and regeneration performance of NiAlNO₃-LDH@NF on Cr（VI） were examined. The experimental results show that NiAlNO₃-LDH@NF with a high specific surface area of layered structure and good crystalline structure were successfully prepared in situ on NF carriers by hydrothermal treatment at 100 ℃ for 48 h under the conditions of Al³⁺/NH₄NO₃ molar ratio of 2:3， solid-liquid ratio of 4.5 mg/mL， and Al³⁺ concentration of 10 mmol/L. The as-prepared NiAlNO₃-LDH@NF was constructed from nanosheets with well-defined shapes and sizes， and the nanosheets have a high specific surface area of layered structure， presenting flower like microspheres composed of numerous LDH nanoplatelets. Under the conditions of 25 ℃， pH=5 and NiAlNO₃-LDH@NF dosage of 3.4 g/L， more than 80% of 50 mg/L Cr（VI） is removed from simulated wastewater within 240 min， and the adsorption capacity is 10.05 mg/g. The adsorption isotherm conforms to Langmuir model， and the adsorption kinetics follows quasi-second-order kinetic equation， which was the surface monolayer adsorption， and adsorption rate is controlled by chemisorption mechanism. After five times of regeneration of NiAlNO₃-LDH@NF， the removal rate of Cr（VI） still reaches 80%~85%， showing its excellent cycle regeneration performance.

Key words: NiAlNO₃-LDH; in situ synthesis; Ni foam; hydrothermal synthesis; adsorption performance; Cr（VI）

CLC Number:

X522

BU Ruiying, XIAO Min, TIAN Jianghao, YANG Xin. In Situ Synthesis of Nickel-Aluminum Hydrotalcite and Its Adsorption Performance on Cr(VI)[J]. Journal of Synthetic Crystals, 2025, 54(11): 2015-2028.

Figures/Tables 19

Table 1 Preparation conditions of samples

Number	Al³⁺/NH₄NO₃ molar ratio	Al³⁺ concentration/ （mmol·L^-1）	Time/h	Temperature/℃	Solid-liquid ratio/（mg·mL^-1）	pH value
Number	Al³⁺/NH₄NO₃ molar ratio	Al³⁺ concentration/ （mmol·L^-1）	Time/h	Temperature/℃	Solid-liquid ratio/（mg·mL^-1）	Before	After
1	2:3	10	48	100	4.50	3.62	5.49
2	2:3	10	6	100	4.50	3.62	3.40
3	2:3	1	48	100	4.50	3.95	7.88
4	1:3	10	48	100	4.50	3.71	5.72
5	2:3	10	48	60	4.50	3.62	5.60
6	2:3	10	48	100	0.75	3.64	4.72
7	1:3	10	24	100	4.50	3.75	5.31

Fig.1 SEM images of NiAlNO3-LDH@NF prepared for different crystallization time. （a1），（a2） NF blank sample；（b1），（b2） 6 h；（c1），（c2） 24 h；（d1），（d2） 48 h

Fig.2 SEM images of NiOOH （a1），（a2） and NiAlNO3-LDH@NF （b1），（b2）

Fig.3 SEM images of NiAlNO3-LDH@NF prepared with different concentrations of Al3+. （a1），（a2） 1 mmol/L；（b1），（b2） 10 mmol/L

Fig.4 SEM images of NiAlNO3-LDH@NF prepared with different solid-liquid ratio. （a1），（a2） 0.75 mg/mL；（b1），（b2） 4.5 mg/mL

Fig.5 SEM images of NiAlNO3-LDH@NF prepared at different crystallization temperatures. （a1），（a2） 60 ℃，（b1），（b2） 100 ℃

Fig.6 SEM images of NiAlNO3-LDH@NF prepared with different molar ratio of Al3+/NH4NO3. （a1），（a2） 1:3；（b1），（b2） 2:3

Fig.7 Effect of preparation conditions on the adsorption properties of Cr（VI） and pH value in the hybrid system before and after hydrothermal synthesis

Fig.8 SEM images of NiAlNO3-LDH@NF before （a） and after （b） adsorption of Cr （VI）（insert corresponds to EDS spectra）

Fig.9 XRD patterns of NF （a） and NiAlNO3-LDH@NF （b）

Fig.10 Effect of pH value on the adsorption performance of Cr（VI）

Fig.11 Effect of adsorption time on the adsorption performance of Cr（VI）

Fig.12 Effect of temperature on the adsorption performance of Cr（VI）

Fig.13 Adsorption isotherms of Cr（VI） adsorption onto NiAlNO3-LDH@NF. （a） Langmuir；（b） Freundlich

Table 2 Adsorption isotherm parameters of NiAlNO3-LDH@NF sample for Cr（VI）

Adsorbent	Langmuir equation			Freundlich equation
Adsorbent	b/（L·mg^-1）	q₀/（mg·g^-1）	R²	K_f/（mg·g^-1）	n	R²
NiAlNO₃-LDH@NF	0.205	9.56	0.997 60	4.17	5.40	0.778 56

Fig.14 Adsorption kinetics models of NiAlNO3-LDH@NF for Cr（VI）. （a） Pseudo-first-order kinics；（b） pseudo-second-order reaction kinetic

Table 3 Pseudo-first-order and pseudo-second-order adsorption kinetic parameters of NiAlNO3-LDH@NF

Adsorbent

Pseudo-first-order kinetics parameter

Pseudo-second-order kinetics parameter

Correlation

coefficient R²

Rate constant k₁

Equilibrium adsorption capacity q_e/（mg·g^-1）

Correlation

coefficient R²

Rate constant k₂

Equilibrium adsorption

capacity q_e/（mg·g^-1）

Fig.15 Reuse performance of NiAlNO3-LDH@NF

Table 4 Comparison of maximum monolayer adsorption capacity and stability for Cr（VI） on in-situ synthesis of LDH materials

Adsorbent	q_max/ （mg·g^-1）	conditions				Regeneration ratio/%	Refence
Adsorbent	q_max/ （mg·g^-1）	C₀/（mg·L^-1）	pH value	t/min	Dosage/（g·L^-1）	Regeneration ratio/%	Refence
MgAlNO₃-LDH@γ-Al₂O₃	22.36	50	6	90	0.6	80	［7］
MgAl-LDH@Graphene	49.34	50	6	1 860	1.0	92.6	［12］
MgAlCO₃-LDH@γ-Al₂O₃	27.80	80	6	300	0.57	90	［22］
NiAlNO₃-LDH@NF	10.05	50	5	90	3.4	80	This work

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