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Nanoconfinement-enhanced lanthanum-biochar composites for simultaneous adsorption and catalytic hydrolysis of organic phosphorus pollutants.

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Title: Nanoconfinement-enhanced lanthanum-biochar composites for simultaneous adsorption and catalytic hydrolysis of organic phosphorus pollutants.
Authors: Xu, Shiyun1 (AUTHOR), Yan, Xing1 (AUTHOR), Wei, Yuchen1 (AUTHOR), Zhang, Yanyang1,2 (AUTHOR) zhangyanyang@nju.edu.cn, Fu, Wanyi1,2 (AUTHOR), Yang, Zhichao1,2 (AUTHOR), Shan, Chao1,2 (AUTHOR), Pan, Bingcai1,2 (AUTHOR)
Source: Water Research. Dec2025:Part B, Vol. 287, pN.PAG-N.PAG. 1p.
Subjects: Catalytic hydrolysis, Organophosphorus compounds, Composite materials, Physisorption, Nanoparticles, Microencapsulation, Eutrophication, Wastewater treatment
Abstract: • La@C enhances NTMP adsorption 85-fold and p -NPP hydrolysis 4.7-fold compared to bulk La(OH)₃. • La@C exhibits wide pH (4–10) applicability with strong anti-interference. • Nanoconfinement in La@C enhances La reactivity and alters P binding mechanisms. • Fixed-bed study show divergent spatiotemporal removal dynamics governed by kinetics. The simultaneous removal of organic phosphorus pollutants (e.g., phosphonates and organophosphate esters (OPEs)) in aquatic systems remains a critical challenge due to their persistence and contribution to eutrophication. Herein, we report a lanthanum-loaded biochar composite (La@C) designed to synergize adsorption and catalytic hydrolysis for efficient organic phosphorus remediation. La@C was synthesized via nitric acid pretreatment of bamboo-derived biochar followed by immobilization of La(OH) 3 nanoparticles under nanoconfinement, achieving uniform dispersion (average size 71 nm) with enhanced reactivity. Batch experiments demonstrated the superior performance of La@C: it exhibited an adsorption capacity of 67.7 μmol/g La for nitrilotris (methylphosphonic acid) (NTMP) and a hydrolysis efficiency of 87.7 % for para-nitrophenyl phosphate (p -NPP), outperforming bulk La(OH)₃ by 54.6 % in capacity (with 85-fold faster kinetics) and 57.7 % in hydrolysis efficiency (with a 4.7-fold higher rate constant), respectively. The composite exhibited wide pH applicability (pH 4–10) and strong resistance to humic acid (20 mg TOC/L) due to nanoconfinement-induced size exclusion and electrostatic shielding. Fixed-bed column experiments revealed spatiotemporal removal dynamics governed by adsorption affinity (orthophosphate> NTMP> p -NPP) and divergent mass transfer zones (MTZ), showcasing a shorter MTZ for orthophosphate and NTMP (0.97 cm) compared to the significantly longer MTZ for p -NPP (280 cm) removal. Mechanistic studies using XPS, solid-state ³¹P NMR, and EXAFS substantiated monodentate inner-sphere complexation for NTMP adsorption and an adsorption-hydrolysis pathway for p -NPP removal. The nanoconfinement effects stabilized the loaded La(OH) 3 nanoparticles, enhanced coordination strength and catalytic activity, offering a scalable strategy for organic phosphorus remediation in complex wastewater matrices. [Display omitted] [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:• La@C enhances NTMP adsorption 85-fold and p -NPP hydrolysis 4.7-fold compared to bulk La(OH)₃. • La@C exhibits wide pH (4–10) applicability with strong anti-interference. • Nanoconfinement in La@C enhances La reactivity and alters P binding mechanisms. • Fixed-bed study show divergent spatiotemporal removal dynamics governed by kinetics. The simultaneous removal of organic phosphorus pollutants (e.g., phosphonates and organophosphate esters (OPEs)) in aquatic systems remains a critical challenge due to their persistence and contribution to eutrophication. Herein, we report a lanthanum-loaded biochar composite (La@C) designed to synergize adsorption and catalytic hydrolysis for efficient organic phosphorus remediation. La@C was synthesized via nitric acid pretreatment of bamboo-derived biochar followed by immobilization of La(OH) 3 nanoparticles under nanoconfinement, achieving uniform dispersion (average size 71 nm) with enhanced reactivity. Batch experiments demonstrated the superior performance of La@C: it exhibited an adsorption capacity of 67.7 μmol/g La for nitrilotris (methylphosphonic acid) (NTMP) and a hydrolysis efficiency of 87.7 % for para-nitrophenyl phosphate (p -NPP), outperforming bulk La(OH)₃ by 54.6 % in capacity (with 85-fold faster kinetics) and 57.7 % in hydrolysis efficiency (with a 4.7-fold higher rate constant), respectively. The composite exhibited wide pH applicability (pH 4–10) and strong resistance to humic acid (20 mg TOC/L) due to nanoconfinement-induced size exclusion and electrostatic shielding. Fixed-bed column experiments revealed spatiotemporal removal dynamics governed by adsorption affinity (orthophosphate> NTMP> p -NPP) and divergent mass transfer zones (MTZ), showcasing a shorter MTZ for orthophosphate and NTMP (0.97 cm) compared to the significantly longer MTZ for p -NPP (280 cm) removal. Mechanistic studies using XPS, solid-state ³¹P NMR, and EXAFS substantiated monodentate inner-sphere complexation for NTMP adsorption and an adsorption-hydrolysis pathway for p -NPP removal. The nanoconfinement effects stabilized the loaded La(OH) 3 nanoparticles, enhanced coordination strength and catalytic activity, offering a scalable strategy for organic phosphorus remediation in complex wastewater matrices. [Display omitted] [ABSTRACT FROM AUTHOR]
ISSN:00431354
DOI:10.1016/j.watres.2025.124445