界面工程构建CoP/磷氮多孔炭实现镉铅同步高灵敏检测研究

doi:10.19964/j.issn.1006-4990.2025-0118

Abstract

Abstract:

To meet the demand for rapid detection of heavy metal ions in water，a novel electrochemical sensing platform based on phosphorus-doped cobalt phosphide modified phosphorus and nitrogen co-doped porous carbon tubes（CoP@P-N-C-550） was developed through a hydrothermal-carbonization-phosphidation coupled strategy.The electronic structure of the material was innovatively regulated by heteroatom doping and metal phosphide synergistic effect，and combined with the mass transfer advantage of the porous carbon tube morphology，the electron transfer efficiency at the electrode interface was significantly improved.The experimental results showed that in single-ion detection，the sensitivity for Cd²⁺ was 15.226 4 μA/（μmol/L） in the range of 0.05~6.00 μmol/L（LOD=5.36 nmol/L），and for Pb²⁺，it was 26.773 6 μA/（μmol/L） in the range of 0.50~6.00 μmol/L（LOD=3.13 nmol/L）.In simultaneous detection of two ions，the sensitivity for Pb²⁺ was increased to 37.008 8 μA/（μmol/L） and LOD was decreased to 2.20 nmol/L，effectively avoiding ion interference.The sensor exhibited excellent repeatability（RSD<2.4% for 10 preparations in detecting Cd²⁺ and Pb²⁺），and achieved high-precision recovery of Cd²⁺（91.00%~104.00%） and Pb²⁺（87.00%~104.33%） in real water samples（mineral and tap water），overcoming the traditional electrode's matrix interference bottleneck.This work provided a new strategy of interface engineering optimization for simultaneous detection of multiple metal ions and holds important application value in environmental monitoring.

Key words: cobalt phosphide（CoP）, phosphorus-nitrogen co-doped porous carbon tube, Cd²⁺ detection, Pb²⁺ detection, electrochemical sensing

CLC Number:

TQ127.11

LI Huiyu, YANG Chao, ZHU Baoshun, ZHANG Jin, CHENG Zhihan, OUYANG Quansheng. Study on interface-engineered CoP/phosphorus-nitrogen porous carbon for simultaneous and highly sensitive detection of Cd²⁺ and Pb²⁺[J]. Inorganic Chemicals Industry, 2025, 57(10): 119-128.

Figures/Tables 11

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样品	元素组成/%
样品	w（C）	w（N）	w（S）	w（H）
P-N-C-550	59.19	27.63	0.15	2.29
CoP@P-N-C-550	31.16	11.33	0.19	1.48

电极	重金属离子	沉积时间/s	单离子检测			同步检测
电极	重金属离子	沉积时间/s	线性范围/ （μmol·L^-1）	灵敏度/［μA/ （μmol·L^-1）］	LOD/ （nmol·L^-1）	线性范围/ （μmol·L^-1）	灵敏度/［μA/ （μmol·L^-1）］	LOD/ （nmol·L^-1）
g-C₃N₄/CNT/NH₂-MIL-88（Fe）^［22］	Cd²⁺	200	—	—	—	0.12~6.00	3.66	39.6
	Pb²⁺		—	—	—	0.02~6.00	19.15	7.6
	Cu²⁺		—	—	—	0.04~6.00	12.15	11.9
	Hg²⁺		—	—	—	0.03~6.00	15.10	9.6
Nitrogen-doped hollow carbon spheres^［23］	Pb²⁺	150	0.05~0.7	6.32	15	—	—	—
	Cu²⁺		0.05~1	5.59	17	—	—	—
	Hg²⁺		0.01~0.9	20.58	2.35	—	—	—
S-doped porous Co₃O₄nanosheets^［24］	Hg²⁺	—	0.2~1.4	1 027.46	16	—	—	—
Fe₂O₃@NCNPs-1.5/GCE^［25］	Cd²⁺	150	1.0~4.0	13.12	38.20	0.5~2.5	14.41	18.79
Fe₂O₃@NCNPs-1.5/GCE^［25］	Pb²⁺	150	0.5~3.5	20.62	27.45	0.5~2.5	22.52	4.92
Ag@ZIF-1000/GCE^［26］	Cd²⁺	320	0.3~3	4.757	14.63	0.3~3	3.542	—
Ag@ZIF-1000/GCE^［26］	Pb²⁺	320	0.3~3	8.907	7.28	0.3~3	7.065	—
CoP@P-N-C-550	Cd²⁺	150	0.05~6.00	15.226 4	5.36	0.25~3.00	3.670 9	22.88
CoP@P-N-C-550	Pb²⁺	150	0.50~6.00	26.773 6	3.13	0.25~3.00	37.008 8	2.20

水样	金属离子	添加浓度/（μmol/L）	检测浓度/（μmol/L）	加标回收率/%
矿泉水	Cd²⁺	0.00	0.00
		1.00	0.91	91.00
		2.00	1.99	99.50
		3.00	2.95	98.33
	Pb²⁺	0.00	0.00
		1.00	0.87	87.00
		2.00	1.94	97.00
		3.00	3.07	102.33
自来水	Cd²⁺	0.00	0.00
		1.00	0.96	96.00
		2.00	2.07	103.50
		3.00	3.12	104.00
	Pb²⁺	0.00	0.00
		1.00	1.00	100.00
		2.00	2.07	103.50
		3.00	3.13	104.33

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Study on interface-engineered CoP/phosphorus-nitrogen porous carbon for simultaneous and highly sensitive detection of Cd²⁺ and Pb²⁺

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Study on interface-engineered CoP/phosphorus-nitrogen porous carbon for simultaneous and highly sensitive detection of Cd2+ and Pb2+