An Iron-Based High-Entropy Alloy with Highly Efficient Degradation for p-Nitrophenol

doi:10.1007/s40195-022-01402-w

Abstract

Abstract:

High-entropy alloys (HEAs) have attracted widespread attention due to their excellent mechanical properties. However, their functional properties arising from the supersaturated solid solution state can be improved. Advanced oxidation processes (AOPs) are considered to be an effective method for decomposing organic pollutants, and HEAs are proposed as effective candidates for AOP catalysts. Currently, several HEAs used for organic pollutant degradation are prepared through mechanical alloying. In this work, FeAlCoNi and FeAlCoNiB Fenton-like catalysts were prepared by single roll melt spinning and subsequent ball milling techniques. We found that the FeAlCoNiB HEA exhibits highly efficient degradation for p-nitrophenol (p-NP). The degradation efficiency of FeAlCoNiB is 120 times higher than that of FeAlCoNi, which confirms that boron functions effectively during the degradation process. FeAlCoNiB has a better degradation efficiency than pure iron powder and a degradation efficiency comparable to that of the amorphous Fe₇₈Si₁₁B₁₁ alloy. Additionally, the degradation efficiency of FeAlCoNiB_X increases (k values from 0.13 to 0.55 min^-1) when the boron content increases from an X value of 0.25 to 1.25. We speculate that Fe₂B favors the degradation process and promotes zero-valent iron to decompose organic pollutants through a galvanic cell effect. Possible p-NP degradation pathways are proposed after LC-MS analysis. This study provides a new series of HEA Fenton-like catalysts, which have the potential to be prepared into bulk devices for industrial applications.

Key words: High-entropy alloys (HEAs), Advanced oxidation processes (AOPs), Galvanic cell effect, Degradation, Organic pollutants

Shenghui Xie, Xiang Liao, Xierong Zeng, Haipeng Yang, Liang He. An Iron-Based High-Entropy Alloy with Highly Efficient Degradation for p-Nitrophenol[J]. Acta Metallurgica Sinica (English Letters), 2022, 35(10): 1653-1664.

Figures/Tables 12

Fig. 1 XRD patterns of the FeAlCoNi, FeAlCoNiB HEAs, pure iron and amorphous Fe78Si11B11 powders

Fig. 2 SEM morphologies of a the FeAlCoNi HEA powder, b the FeAlCoNiB HEA powder, c the Fe78Si11B11 amorphous powder, d pure iron powder; inset with the corresponding particle profile image

Fig. 3 Particle size distributions of a the FeAlCoNi HEA powder, b the FeAlCoNiB HEA powder, c the amorphous Fe78Si11B11 powder, d pure iron powder

Fig. 4 p-NP decolorization by the FeAlCoNi, FeAlCoNiB HEA powders, amorphous Fe78Si11B11 powder and pure iron powder. a UV absorption spectra of p-NP solution during degradation by FeAlCoNiB. b Comparison of p-NP degradation rates calculated by Eq. 2; inset with complete curve of FeAlCoNi HEA.c A first-order kinetic fitting curve of the p-NP concentration during the degradation process obtained by fitting with Eq. 3; inset with complete curve of FeAlCoNi HEA. d Reaction kinetics constant k of the degradation reaction by different catalysts

Table 1 Decolorization parameters of p-NP by FeAlCoNi, FeAlCoNiB HEA powders, amorphous Fe78Si11B11 powder and pure iron powder

Sample	C₀ (mg L^-1)	D_5min (5 min)	D_ultimate (30 min)	k (min^-1)	t_1/2 (min)	R² (%)
Fe	20	49.7	98.5	0.16	4.50	98.9
Fe₇₈Si₁₁B₁₁	20	85.8	97.3	0.38	1.70	99.4
FeAlCoNiB	20	85.6	97.5	0.36	1.81	99.8
FeAlCoNi	20	3.2	8.3	0.003	289	99.7

Fig. 5 SEM characterization of the surface morphology of the FeAlCoNiB HEA powder a before reaction, b after reaction; inset with the corresponding particle profile image

Fig. 6 XPS characterization of the surface of the FeAlCoNiB HEA powder a before reaction, b after reaction

Fig. 7 a-e SEM morphologies of FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25); inset with the corresponding particle profile image. f-j Particle size distributions of FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25)

Fig. 8 XRD patterns and decolorization results of p-NP by FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25). a XRD patterns of FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25). b Decolorization ratio of p-NP by FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25). c Fitted curves of the p-NP concentration during the degradation process by FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25). d The k values of the degradation reaction by FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25). e Efficiency of degradation by reused FeAlCoNiB1.25. f The k values of degradation by reused FeAlCoNiB1.25

Table 2 Decolorization parameters of the p-NP by FeAlCoNiBX (X = 0.25, 0.5, 0.75, 1.0, 1.25)

Sample	C₀ (mg L^-1)	D_5min (5 min)	D_ultimate (30 min)	k (min^-1)	t_1/2 (min)	R² (%)
FeAlCoNiB_0.25	20	49.1	95.5	0.13	5.60	99.3
FeAlCoNiB_0.5	20	65.5	95.9	0.23	3.16	99.8
FeAlCoNiB_0.75	20	69.3	95.9	0.27	2.73	99.8
FeAlCoNiB_1.0	20	85.5	97.5	0.36	1.98	99.6
FeAlCoNiB_1.25	20	94.7	97.2	0.55	1.31	99.9

Fig. 9 Open circuit potentials (OCPs) of NiAl, Fe and Fe2B

Fig. 10 Mass spectrometry of a p-NP solution and the intermediates during degradation at b 5 min, c 30 min. d Possible pathways for p-NP degradation

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