双功能核壳Cu2O@NiFe2O4 Z型纳米反应器光辅助电催化同步氧化-还原合成鸟粪石

doi:10.1016/S1872-2067(25)64755-3

摘要/Abstract

摘要：

地表水中次磷酸盐(H₂PO₂^-)和硝酸盐(NO₃^-)的过量积累会刺激浮游植物异常增殖, 引发水体富营养化与水质恶化. 尤其是NO₃^-可被还原为毒性更强的亚硝酸盐(NO₂^-), 对环境和人体健康构成严重威胁. 因此, 开发将磷和氮协同回收为磷酸铵镁(MgNH₄PO₄, 俗称鸟粪石)的“一石二鸟”策略, 在环境修复与资源循环利用方面意义重大. MgNH₄PO₄在制药工业中广泛用作药物原料或添加剂; 在农业领域, 其作为缓释肥料可长效供应铵态氮、磷及镁元素, 不仅能有效控制氮素损失, 还能补充镁离子以提升作物品质. 基于此, 亟需开发一种绿色低碳的新型合成方法,直接利用含NO₃^-和H₂PO₂^-的废水生产高附加值鸟粪石, 从而实现废水中氮磷资源的同步高效回收.

光辅助电催化(PA-EC)过程结合了光催化和电催化方法的优势, 在水体修复和资源回收方面比单一过程更为有效. 在PA-EC过程, 氧化和还原反应可以借助光生空穴和电子在阳极和阴极上同时发生, 这为从含有NO₃^-和H₂PO₂^-的废水中直接合成MgNH₄PO₄提供了独特优势. 双功能催化剂的研究有望简化合成过程并降低催化剂成本. 本文以镍泡沫(NF)上原位生长的Cu₂O为模板, 通过化学刻蚀和低温煅烧构建了蛋黄-壳结构Cu₂O@NiFe₂O₄/NF Z型异质结纳米反应器阵列. 该Z型异质结可以保留两个不同半导体中的高能电子和空穴, 具有强氧化还原能力, 可满足同步氧化还原反应的需求. 蛋黄-壳Z型异质结的空隙限域效应可以提高电子转移效率并增强反应物的富集, 从而促进PA-EC反应. 氧空位不仅调节了催化剂的内在电子特性, 还作为活性位点增强了反应物的吸附和活化. 更重要的是, 异质结构界面产生的内建电场在促进特定离子的表面吸附和增强电荷转移过程中起着关键作用, 能够提高催化活性. 这一机制已在其他催化反应中得到广泛探索, 如析氧反应、氧还原反应和CO₂还原反应. 所构建的PA-EC系统使用蛋黄-壳结构的Cu₂O@NiFe₂O₄ Z型异质结作为阴阳两极的光电催化材料, 并分别评估了其在光辅助电催化硝酸盐还原和H₂PO₂^-氧化的过程中的性能. Janus Cu₂O@NiFe₂O₄/NF光阴极在-1.6 V (vs NHE)下达到了~92.31%的最大法拉第效率和38.06 mmol L^-1的NH₃产量, 而Cu₂O@NiFe₂O₄/NF光阳极上H₂PO₂^-的转化率也可达到98%. 混合阴阳极产物并加入镁离子可实现N、P共回收, 生产MgNH₄PO₄肥料.

综上, 本研究设计了一种集成的PA-EC策略, 通过同步驱动NO₃^-的光辅助电还原与H₂PO₂^-的光辅助电氧化两个半反应, 实现了从含NO₃^-和H₂PO₂^-废水中回收N、P合成MgNH₄PO₄, 为实现可再生N、P资源高效且具有成本效益的PA-EC集成转化为有价值的化学品提供了新思路.

关键词: 硝酸盐还原, 次磷酸盐氧化, 鸟粪石光辅助电催化合成, 营养物回收, 废水处理

Abstract:

In this study, we developed a tandem photo-assisted electrochemical (PA-EC) chemical strategy for both energy-saving ammonia/fertilizer synthesis and comprehensive nitrogen- and phosphorus-rich wastewater treatment, in which synchronous hypophosphite ion (H₂PO₂^-) oxidation to phosphate ion (PO₄^3-) (POR) and nitrate reduction (NO₃RR) to ammonia (NH₃) occur, followed by cascade chemical precipitation to generate struvite. Herein, a bifunctional Cu₂O@NiFe₂O₄ Z-scheme heterojunction with a yolk/shell structure and oxygen vacancies (O_Vs) was designed and developed to optimize the NO₃RR/POR. Serving as a key component, the established PA-EC system consisted of a Janus Cu₂O@NiFe₂O₄/NF self-supporting integrated photocathode and a Cu₂O@NiFe₂O₄/NF photocathode with efficient struvite PA-EC synthesis performance under a low cell voltage of 1.6 V vs NHE. Specifically, Janus Cu₂O@NiFe₂O₄/NF photocathode exhibits superior performance with a high NH₃ yield of 38.06 mmol L^-1 and a faradaic efficiency (FE) of 92.31% at 1.6 V vs. NHE and enables ammonia FE over 60% in a broad NO₃^- concentration window of 0.005-0.5 mol L^-1. The photoassisted electrochemical catalytic mechanism and reaction pathway for struvite synthesis on Cu₂O@NiFe₂O₄ were investigated through a series of experiments and theoretical calculations. The results demonstrated the critical roles of the interfacial electric field, void confinement, and oxygen vacancies in promoting the overall catalytic efficiency. These encouraging results warrant further studies on combined P and N recovery for efficient production of valuable fertilizers.

Key words: Nitrate reduction, Hypophosphite oxidation, Struvite photo-assisted electrocatalysis, Nutrient recovery, Wastewater treatment

孙燕, 张蕾. 双功能核壳Cu₂O@NiFe₂O₄ Z型纳米反应器光辅助电催化同步氧化-还原合成鸟粪石[J]. 催化学报, 2025, 76: 230-241.

Yan Sun, Lei Zhang. Sustainable photo-assisted electrocatalysis of struvite fertilizer via synchronous redox catalysis on bifunctional yolk-shell Cu₂O@NiFe₂O₄ Z-scheme nanoreactor[J]. Chinese Journal of Catalysis, 2025, 76: 230-241.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64755-3

https://www.cjcatal.com/CN/Y2025/V76/I9/230

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Scheme 1. Schematic illustration of struvite fertilizer synthesis and utilization.

Scheme 2. Schematic diagram of the synthesis process for the self-supporting Cu2O@NiFe2O4/NF integrated photoelectrode.

Fig. 1. SEM images of Cu2O/NF (a1), Cu2O@NiFe2O4/NF (b1), and NiFe2O4/NF (c1). SEM images of Cu2O (a2), Cu2O@NiFe2O4 (b2) and NiFe2O4 (c2). TEM images of Cu2O (a3), Cu2O@NiFe2O4 (b3-b5) and NiFe2O4 (c3). (b5) EDS mapping of Cu2O@NiFe2O4.

Fig. 2. (a) XRD patterns of catalysts. High-resolution XPS spectra of Ni 2p (b), Fe 2p (c), Cu 2p (d), and O 1s (e). (f) Tauc’s bandgap plots. (g) Mott-Schottky plots. (h) Schematic illustration of space-charge region at the contact zone of Cu2O and NiFe2O4 heterojunction.

Fig. 3. (a) LSVs of catalysts in 50 mmol L-1 NaNO3 and 0.5 mol L-1 Na2SO4. (b) PL spectra. (c) Transient photocurrent responses of catalysts. (d) NH3 yield. (e) EIS Nyquist plots. (f) Catalysts with different hollow void; the OCP change of Cu2O@NiFe2O4 with different hollow void in 0.5 mol L-1 Na2SO4 and 0.5 mol L-1 Na2SO4 + 50 mmol L-1 NaNO3 solution. (g) Yield of NH3 of photocathode with different sprayed times. (h) CA of photocathode. (i) NH3 yield and FE of NO3RR for Janus Cu2O@NiFe2O4/NF photocathode at different potentials.

Fig. 4. (a) Time-dependent concentration changes of NO3--N, NH3-N, and NO2--N by Janus Cu2O@NiFe2O4/NF photocathode (b) YieldNH3 and FENH3 of Janus Cu2O@NiFe2O4/NF photocathode with concentrations of NO3- ranging from 5 to 0.5 mol L-1. (c) Stability test of Janus Cu2O@NiFe2O4/NF photocathode for 10-h continuous NO3RR. (d) Comparison of the NO3RR performance of the Janus Cu2O@NiFe2O4/NF with other catalysts reported in the literature.

Fig. 5. (a) The logarithm of jNH3 at the potential of -0.8 V vs. NHE as a function of the logarithm cNO3- on the Cu2O, NiFe2O4, Cu2O@NiFe2O4. Finite element simulation result: Surface NO3- density distribution (b); Electric field distribution (c); Surface potential distribution (d). Around the yolk-shell model (left); the nanocube model (right).

Fig. 6. (a) Double layer capacitance for the Cu2O, NiFe2O4 and Cu2O@NiFe2O4 electrodes with/without 50 mmol L-1 NaNO3 in 0.5 mol L-1 Na2SO4 electrolyte based on the CVs at various scan rates. (b) Zeta potentials of Cu2O, NiFe2O4 and Cu2O@NiFe2O4. (c) FTIR of Cu2O@NiFe2O4 before and after illumination. (d) EPR spectra of the solutions obtained after 10 min of photocatalysis by Cu2O@NiFe2O4 at light or dark using DMPO as the *H-trapping reagent. (e) The evolutions of NO2- along with the reaction time during NO3RR conducted by different electrodes (left), yieldNH3 of NO2RR for Janus Cu2O@NiFe2O4/NF photocathode (right). (f) Koutecky-Levich plots of Cu2O@NiFe2O4.

Scheme 3. Schematic illustration of the role of IEF and confinement effect for NO3RR.

Fig. 7. (a) LSVs of Cu2O, NiFe2O4 and Cu2O@NiFe2O4 for POR. (b) Conversion rate of H2PO2− at various voltages. (c) i-t curve and conversion rate of H2PO2− over Cu2O@NiFe2O4 electrode for consecutive cycles at 2.2V vs. NHE. (d) Schematic illustration of the PEC system for NO3RR and the POR. (e) LSV curves of the Cu2O@NiFe2O4 electrode as the cathode and anode in NO3RR||POR and NO3RR||OER. (f) NH3 yield rate, NH3 FE and H2PO2− conversion rate of the Cu2O@NiFe2O4 electrode in NO3RR||POR at various voltages. (g) XRD of the N-P precipitates. (h) Effect of MgNH4PO4 on soybean growth.

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双功能核壳Cu₂O@NiFe₂O₄ Z型纳米反应器光辅助电催化同步氧化-还原合成鸟粪石

Sustainable photo-assisted electrocatalysis of struvite fertilizer via synchronous redox catalysis on bifunctional yolk-shell Cu₂O@NiFe₂O₄ Z-scheme nanoreactor

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