现代化工

现代化工 ›› 2026, Vol. 46 ›› Issue (2) : 211-216. DOI: 10.16606/j.cnki.issn0253-4320.2026.02.033

科研与开发

花状氧化铜的制备及其光类芬顿降解四环素研究

周兵利 ^* ,
李倩

作者信息 +

Preparation of flower-like copper oxide and its photo-like fenton degradation performance of tetracycline

ZHOU Bing-li ^* ,
LI Qian

Author information +

文章历史 +

Received		Published
2025-05-13		2026-02-20
Issue Date	Revised Date
2026-02-11	2025-05-13

PDF (6240K)

摘要

以泡沫铜(Cu Foam)为原料,在过硫酸钠(PDS)和氢氧化钠(NaOH)混合溶液中氧化形成中间体Cu(OH)₂纳米线,之后在高温下加热制备出花状Cu@CuO,用于高效活化过硫酸盐(PMS)光降解四环素(TC)。采用SEM(扫描电子显微镜)、EDS(能量散射光谱)、XRD(X射线衍射)、Raman(拉曼光谱)和XPS(X射线光电子能谱)对Cu@CuO进行了表征,探究了反应体系、PMS投加量、pH对TC降解率的影响。通过自由基猝灭实验,推测了Cu@CuO活化PMS光降解TC的机理。结果表明,Cu@CuO在PMS投加量0.05 g、pH=7以及光照的条件下,Cu@CuO/PMS/light体系具有最佳降解效果。在10 min时,TC的降解率高达96.81%。Cu@CuO/PMS/light体系在降解TC过程中,主要产生了 ¹O₂、

· O 2 -

、h⁺、·OH和

S O 4 · -

等活性物种,Cu@CuO/PMS/light体系通过自由基(

S O 4 · -

、·OH、

· O 2 -

)与非自由基(e^-、h⁺、¹O₂)途径降解TC。豆芽生长情况实验表明降解后水毒性降低。

Abstract

Copper foam (Cu Foam) was utilized as a precursor for oxidation in a mixed solution of sodium persulfate (PDS) and sodium hydroxide (NaOH),resulting in the formation of Cu(OH)₂ nanowires as intermediate products.Subsequently,flower-like Cu@CuO was synthesized via high-temperature treatment and employed for the efficient activation of peroxymonosulfate (PMS) in the photodegradation of tetracycline (TC).The Cu@CuO was characterized using SEM,EDS,XRD,Raman spectroscopy and XPS.The effects of reaction system such as PMS dosage,and pH on the degradation rate of tetracycline (TC) were also investigated.The mechanism of Cu@CuO-mediated PMS activation for the photodegradation of tetracycline (TC) was hypothesized through radical quenching experiments.The results indicated that the Cu@CuO/PMS/light system exhibited optimal degradation performance under the conditions of 0.05 g PMS dosage,pH=7,and light irradiation.Under the conditions of 10 minutes,the degradation rate of tetracycline (TC) reached as high as 96.81%.During the degradation of TC,the Cu@CuO/PMS/light system predominantly generated reactive species such as ¹O₂, $· O 2 -$ ,h⁺,·OH and $S O 4 · -$ .The Cu@CuO/PMS/light system degraded TC through both radical ( $S O 4 · -$ ,·OH, $· O 2 -$ ) and non-radical (e^-,h⁺,¹O₂) pathways.The bean sprout growth experiment demonstrated that the water after degradation showed less toxicity.

Graphical abstract

关键词

泡沫铜 / 四环素 / 过一硫酸盐 / 光类芬顿 / Cu@CuO

Key words

Cu foam / tetracycline / peroxymonosulfate / photo-like fenton / Cu@CuO

引用本文

引用格式 ▾

[Author(id=1241417641396498842, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=LYZBL91166@163.com, emailSecond=null, emailThird=null, correspondingAuthor=1, authorType=1, ext={EN=AuthorExt(id=1241417641421664668, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, authorId=1241417641396498842, language=EN, stringName=Bing-li ZHOU, firstName=Bing-li, middleName=null, lastName=ZHOU, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=^*, address=Luoyang Ecological Environment Monitoring Center of Henan Province, Luoyang 471000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241417641442636189, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, authorId=1241417641396498842, language=CN, stringName=周兵利, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=^*, address=河南省洛阳生态环境监测中心,河南洛阳 471000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241417641362944406, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, xref=null, ext=[AuthorCompanyExt(id=1241417641367138711, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, companyId=1241417641362944406, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Luoyang Ecological Environment Monitoring Center of Henan Province, Luoyang 471000, China), AuthorCompanyExt(id=1241417641375527320, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, companyId=1241417641362944406, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=河南省洛阳生态环境监测中心,河南洛阳 471000)])]), Author(id=1241417641463607711, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, orderNo=1, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=null, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1241417641492967841, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, authorId=1241417641463607711, language=EN, stringName=Qian LI, firstName=Qian, middleName=null, lastName=LI, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=Luoyang Ecological Environment Monitoring Center of Henan Province, Luoyang 471000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241417641513939362, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, authorId=1241417641463607711, language=CN, stringName=李倩, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=河南省洛阳生态环境监测中心,河南洛阳 471000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241417641362944406, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, xref=null, ext=[AuthorCompanyExt(id=1241417641367138711, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, companyId=1241417641362944406, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Luoyang Ecological Environment Monitoring Center of Henan Province, Luoyang 471000, China), AuthorCompanyExt(id=1241417641375527320, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720280999391879, companyId=1241417641362944406, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=河南省洛阳生态环境监测中心,河南洛阳 471000)])])] 周兵利,李倩. 花状氧化铜的制备及其光类芬顿降解四环素研究[J]. 现代化工, 2026, 46(2): 211-216 DOI:10.16606/j.cnki.issn0253-4320.2026.02.033

登录浏览全文

4963

注册一个新账户忘记密码

在过去几十年中,非生物降解有机污染物排放引发的水污染,尤其是抗生素类四环素作为高生物毒性的有害物质,已成为对生态环境和人类健康的严重威胁^[1-2]。由于常规废水处理过程的净化效率有限,抗生素污染物常常出现在地表水和地下水中^[3-4]。因此,研究者提出了多种去除水体中抗生素的技术,其中过硫酸盐高级氧化法(AOPs)被广泛认为是一种有效的水体污染物去除方法^[3,5]。传统上,过氧化单硫酸盐(PMS)或过二硫酸盐(PDS)的活化通过电子或能量转移裂解过氧键(O—O),从而生成高活性氧物种(ROS)以促进污染物的降解^[6]。

通过非均相催化过程活化PMS以产生活性物种(ROS)的研究已得到广泛关注^[7-8]。由于金属基催化剂在不同价态之间具有高效的电荷转移能力,并且稀土元素的丰度进一步增强了其催化性能,金属基催化剂已被证明是有效的PMS活化剂^[9]。CuO作为一种典型的过渡金属氧化物,具有多种形态结构和较强的电子转移能力,已被广泛应用于PMS的有效活化^[10-11]。

本研究制备了以泡沫铜(Cu Foam)为原料的花状Cu@CuO催化剂,并通过PMS活化在降解TC污染物中表现出优异的催化性能。对Cu@CuO催化剂的形貌结构、降解效率、电子转移情况、降解过程中产生的自由基、降解机理以及四环素(TC)降解产物的毒性进行了全面的研究。

1 实验部分

1.1 试剂与仪器

过硫酸钠(PDS)、NaOH、HCl、甲醇(MeOH)、叔丁醇(TBA)均购自天津天力化学试剂有限公司。草酸铵(AO)购自天津科密欧化学试剂有限公司。过硫酸氢钾(PMS)、对苯醌(p-BQ)、组氨酸(L-His)均购自上海麦克林生化科技有限公司。Cu Foam购自苏州科盛和金属材料有限公司。

Quanta250 FEG型扫描电子显微镜(SEM),FEI捷克有限公司;D8 Advance型X射线衍射仪(XRD),德国Bruker公司;In Via Reflex型激光拉曼光谱仪(Raman),英国Renishaw公司;Kratos AXIS Ultra DLD型X射线光电子能谱(XPS),英国Kratos公司;BeNano 180 Zeta型电化学工作站,武汉科思特仪器股份有限公司。

1.2 样品制备

Cu@CuO制备:采用HCl溶液(质量分数为37%)、乙醇和去离子水依次清洗Cu Foam(2.0 cm×3.0 cm)15 min,进行预处理,以去除表面氧化物层,随后在60℃烘箱中彻底干燥。在典型程序中,搅拌下将80.0 mL 4 mol/L NaOH与0.187 5 mol/L PDS溶液混合,直至溶液变为透明。然后将预处理后的Cu Foam(2 cm×3 cm)在室温下浸入上述混合溶液中约20 min。反应后,取出蓝色Cu@Cu(OH)₂纳米线,用乙醇和去离子水洗涤3次,然后在60℃的真空干燥箱中干燥,得到Cu@Cu(OH)₂前驱体。再将Cu@Cu(OH)₂前驱体置于200℃真空干燥箱中加热2 h,使Cu(OH)₂脱水转化为CuO,得到 Cu@CuO催化剂。

1.3 测试与表征

采用SEM、EDS(能量色散X射线光谱)、XRD、Raman对样品形貌结构进行表征;采用XPS分析样品表面价态分布;利用电化学工作站对样品进行电化学阻抗谱(EIS)测试。

1.4 光催化实验

在磁力搅拌烧杯中进行,使用300 W氙灯模拟可见灯光,依据TC降解率评估Cu@CuO催化剂在活化PMS中的催化活性。详细地,将2 cm×3 cm Cu@CuO加入到100 mL TC(10 mg/L)中,在室温下搅拌30 min以达到吸附-解吸平衡后,加入一定量的PMS,使用1 mol/L NaOH或HCl调节溶液的pH,同时开启光源开始反应。反应开始后,在一定的时间间隔(2、4、6、8、10 min),收集3 mL反应悬浮液并用0.22 μm过滤器过滤,使用紫外分光光度计在357 nm处测量溶液的吸光度。

在TC降解实验的基础上,添加相对应的牺牲剂检测自由基。

2 结果和讨论

2.1 Cu@CuO的结构表征

2.1.1 XRD和Raman分析

图1(a)为Cu Foam的XRD图,在43.2、50.3°和74.4°处具有3个强衍射峰,其属于Cu Foam中的金属铜(JCPDS 04—0836)。图1(b)为Cu@CuO的XRD图,其中在2θ为35.5°和38.9°处的衍射峰与CuO的标准XRD图案一致(JCPDS 48—1548),证明Cu@CuO制备成功。

Raman光谱进一步证实了CuO的成功制备(图2)。在纯的Cu Foam上并未观察到任何峰,但Cu@CuO样品包含3个主峰,分别为280、320 cm^-1和621 cm^-1。最强的拉曼峰在280 cm^-1处归属于A_g模式,而较弱的拉曼峰在320 cm^-1和621 cm^-1处归属于B_g模式。

2.1.2 SEM分析

图3(a)展示了Cu Foam的SEM形貌,材料表面整体平整,局部区域存在少量孔状结构。图3(b)为Cu@Cu(OH)₂的SEM图,在碱性环境中Cu Foam被氧化生成Cu@Cu(OH)₂纳米线。经过高温处理后,Cu@Cu(OH)₂前驱体变成由纳米线支撑的花状Cu@CuO的复合结构[图3(c)]。

通过EDS面分布图谱验证了样品中含有Cu和O两种化学元素(图4)。从图4(a)~(c)中可以看出,Cu和O元素均匀分布于样品中,Cu元素质量分数和原子分数分别为67.79%和33.34%,O元素质量分数和原子分数分别为26.44%和51.65%。

2.1.3 XPS分析

图5为Cu@CuO的XPS图谱,对Cu和O的高分辨XPS图谱进行拟合分析。图5(a)中在932.5 eV和952.9 eV处的2个峰具有20 eV的能量差,分别属于Cu 2p_3/2和Cu 2p_1/2。Cu 2p_3/2信号可以拟合成在932.5 eV和934.0 eV处的2个峰,在952.9 eV和954.2 eV处的2个峰代表Cu 2p_1/2信号。在932.5 eV和952.9 eV处的峰可以归因于样品中Cu的Cu⁺/Cu⁰,而在934.0 eV和954.2 eV处的2个峰可以归因于样品中CuO的Cu²⁺,此外,可以观察到在941.5、944.0 eV和962.3 eV处的峰属于3个卫星峰^[12]。图5(b)中O 1s的高分辨率光谱显示了分别归因于晶格氧(O_L)和表面羟基氧(O_H)的529.85 eV和531.4 eV处的2个最大峰^[13-14]。

2.2 Cu@CuO的性能研究

2.2.1 不同体系对降解TC影响分析

图6显示了TC在不同反应体系中的降解率。在无催化剂和PMS的情况下,TC的降解可以忽略不计。仅PMS存在时,凭借其固有氧化能力,10 min内降解了19.88%的TC^[15],Cu Foam/PMS/dark体系下降解效率略微增加,而Cu@CuO/PMS/dark体系中TC的降解效率明显提高,反应10 min后,降解效率为64.94%。在光照条件下,Cu Foam/PMS/light存在下降解效率增加至62.78%,而Cu@CuO/PMS/light体系中TC的降解效率在10 min为80.5%。这可能是因为Cu@CuO具有较强的电子传递能力,能够促进反应中电子的快速转移。这对于氧化还原反应至关重要,尤其是在PMS分解过程中,Cu@CuO能够有效地促进电子与氧化剂之间的转移,从而增强其降解性能。

2.2.2 初始条件对Cu@CuO/PMS/light体系降解TC的影响分析

本研究考察了PMS浓度、溶液pH对Cu@CuO活化PMS降解TC效率的影响。图7实验结果表明,PMS浓度从0.01 g增加至0.05 g,在10 min内降解效率从68.62%提高到96.81%,可能原因为PMS和Cu@CuO的接触机会增加,产生更多活性物种^[16]。然而,PMS浓度进一步增加至0.3 g/L时,TC降解性能降低,这是因为PMS的自猝灭效应,以及TC和过量PMS之间与反应性物质相互作用的竞争的结果^[17]。因此,最佳PMS浓度确定为0.05 g。初始pH也是影响Cu@CuO/PMS/light体系催化性能的关键参数^[18]。在pH为3~9的范围内,该体系对TC的降解率超过95.11%,表明该体系对pH范围较宽的废水具有潜在的净化作用。值得注意的是,Cu@CuO/PMS/light系统在酸性环境中(pH=3)的TC降解率略高于其他环境中的TC降解率。这可能归因于大量的H⁺离子被Cu@CuO催化剂的氧化表面消耗并溶解,这又产生了更多的原位低价 Cu(Ⅰ)并加速PMS活化^[19-20]。

2.2.3 电化学测试分析

此外,电化学阻抗谱(EIS)测试在开路电位下进行(图8)。通过EIS谱图,得出了电荷转移电阻(R_ct)值。Cu@CuO的R_ct值为1.98 Ω,低于Cu Foam(3.15 Ω)。这表明Cu@CuO显著提高了电子转移速率,从而促进了活性物种的生成。

进行猝灭实验以评估Cu@CuO/PMS/light体系中产生的活性物种。MeOH通常用于猝灭

S O 4 · -

和 ·OH,而TBA与·OH的反应性高于

S O 4 · -

^[21]。如图9所示,添加MeOH和TBA(200 mmol/L)对Cu@CuO/PMS/light体系中TC消除率分别为79.17%和74.58%,表明

S O 4 · -

和·OH在TC降解时参与反应。当向反应溶液中引入

· O 2 -

的优先捕获剂p-BQ时,达到了70.26%的抑制效果,这有助于

· O 2 -

参与TC降解^[22-23]。然而,具有低还原电位(-0.28 V)的

· O 2 -

自由基不能直接氧化污染物^[22]。

· O 2 -

的形成可能会产生¹O₂^[24]。值得注意的是,反应中L-His(一种有效的 ¹O₂牺牲剂)的存在有效地将TC降解的影响降低至仅57.16%,表明 ¹O₂对TC去除贡献较大^[25]。此外,添加200 mmol/L的AO(作为e^-的牺牲剂,在10 min内降解64.33%,表明在降解过程中也有e^-参与其中。

基于上述分析,我们推测Cu@CuO/PMS/light体系中生成活性物种(ROS)降解TC的机制(图10)。首先,Cu@CuO表面的Cu²⁺可与

H S O 5 -

反应,溶液中生成的Cu⁺进一步与

H S O 5 -

反应生成

S O 4 · -

和·OH,Cu⁰可能充当还原剂以促进Cu²⁺/Cu⁺氧化还原循环,如式(1)~(5)所示;

· O 2 -

则由PMS的水解反应在H₂O的帮助下和e^-转移的作用下生成,如式(6)所示。此外,

· O 2 -

可以与·OH反应,通过方程式(7)形成¹O₂^[26]。这些可能的多重途径生成的ROS能够攻击TC,并最终将中间产物矿化为H₂O和CO₂。

(1)$\mathrm{Cu}^{2+}+\mathrm{HSO}_{5}^{-} \longrightarrow \mathrm{Cu}^{+}+\mathrm{SO}_{5}^{·-}+\mathrm{H}^{+}$

(2)$\mathrm{Cu}^{+}+\mathrm{HSO}_{5}^{-} \longrightarrow \mathrm{SO}_{4}^{·-}+\mathrm{Cu}^{2+}+\mathrm{OH}^{-}$

(3)$\mathrm{SO}_{4}^{·-}+\mathrm{OH}^{-} \longrightarrow \mathrm{SO}_{4}^{2-}+\cdot \mathrm{OH}$

(4)$\mathrm{Cu}^{2+}+\mathrm{Cu}^{0} \longrightarrow 2 \mathrm{Cu}^{+}$

(5)$\mathrm{HSO}_{5}^{-}+\mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{SO}_{4}^{2-}+\cdot \mathrm{O}_{2}^{-}+\mathrm{H}^{+}$

(6)$\mathrm{O}_{2}+\mathrm{e}^{-} \longrightarrow \cdot \mathrm{O}_{2}^{-}$

(7)$\cdot \mathrm{OH}^{+} \cdot \mathrm{O}_{2}^{-} \longrightarrow{ }^{1} \mathrm{O}_{2}+\mathrm{OH}^{-}$

将质量相同且完整的绿豆种子种植在2种溶液中,即TC溶液(10 mg/L)和已经经历Cu@CuO/PMS/light体系处理的相同TC溶液,在25℃的恒温下生长1周。如图11所示,在处理过的TC溶液中的绿豆芽茂盛生长,并且比在TC溶液中的豆芽茂盛得多。此外,从图中明显看出,经处理的TC溶液中的芽的茎的长度比未经处理的TC溶液中的芽的茎的长度长得多,这些结果有力地证明了Cu@CuO/PMS/light体系在降低被TC污染的水体的生物毒性方面的有效性。

3 结论

以Cu Foam为原料,在PDS和NaOH混合溶液中氧化形成中间体Cu(OH)₂纳米线,之后在高温下加热制备出花状Cu@CuO,用于高效活化PMS光降解TC。

(1)Cu@CuO在PMS投加量0.05 g、pH=7、光照条件下,Cu@CuO/PMS/light体系具有最佳降解效果。在10 min内TC的降解率高达96.81%。

(2)Cu@CuO/PMS/light体系在降解TC过程中,主要产生了 ¹O₂、

· O 2 -

、h⁺、·OH和

S O 4 · -

等活性物种,Cu@CuO/PMS/light体系通过自由基(

S O 4 · -

、·OH、

· O 2 -

)与非自由基(e^-、h⁺、¹O₂)途径降解TC。

(3)降解后的水可用于重新种植豆芽,这充分证明了该处理方法对环境友好,未造成明显的毒性或污染影响。

参考文献

原文顺序 | 出版日期 | 本文引用

[1]	Tong X, Mohapatra S, Zhang J, et al. Source,fate,transport and modelling of selected emerging contaminants in the aquatic environment:Current status and future perspectives[J]. Water Research, 2022, 217:118418.

[2]	Guo Z, Kodikara D, Albi L S, et al. Photodegradation of organic micropollutants in aquatic environment:Importance,factors and processes[J]. Water Research, 2023, 231:118236.

[3]	Li Z, Wang J, Chang J, et al. Insight into advanced oxidation processes for the degradation of fluoroquinolone antibiotics:Removal,mechanism,and influencing factors[J]. Science of the Total Environment, 2023, 857:159172.

[4]	邱娅璐, 高鹏, 伏毅, 等. 光催化材料降解抗生素废水研究进展[J]. 化工新型材料, 2025, 53(2):65-71.

[5]	陈燕, 李卫士. 抗生素光催化降解:催化剂的研究进展[J]. 现代化工, 2024, 44(S1):42-46.

[6]	Zhao W, Shen Q, Nan T, et al. Cobalt-based catalysts for heterogeneous peroxymonosulfate (PMS) activation in degradation of organic contaminants:Recent advances and perspectives[J]. Journal of Alloys and Compounds, 2023, 958:170370.

[7]	Hou J, He X, Zhang S, et al. Recent advances in cobalt-activated sulfate radical-based advanced oxidation processes for water remediation:A review[J]. Science of the Total Environment, 2021, 770:145311.

[8]	Zheng X, Niu X, Zhang D, et al. Metal-based catalysts for persulfate and peroxymonosulfate activation in heterogeneous ways:A review[J]. Chemical Engineering Journal, 2022, 429:132323.

[9]	Shi Q, Deng S, Zheng Y, et al. The application of transition metal-modified biochar in sulfate radical based advanced oxidation processes[J]. Environmental Research, 2022, 212:113340.

[10]	Du X, Zhang Y, Si F, et al. Persulfate non-radical activation by nano-CuO for efficient removal of chlorinated organic compounds:Reduced graphene oxide-assisted and CuO (001) facet-dependent[J]. Chemical Engineering Journal, 2019, 356(6):178-189.

[11]	Yan P, Shen J, Wang S, et al. Removal of 2,6-dichlorophenol in water by CuO activated peroxymonosulfate:Efficiency,mechanism and degradation pathway[J]. Separation and Purification Technology, 2021, 254:117630.

[12]	Chen F, Chen C, Hu Q, et al. Synthesis of CuO@CoNi LDH on Cu foam for high-performance supercapacitors[J]. Chemical Engineering Journal, 2020, 401:126145.

[13]	He Y, Zhang J, Zhou H, et al. Synergistic multiple active species for the degradation of sulfamethoxazole by peroxymonosulfate in the presence of CuO@FeO_x@Fe⁰[J]. Chemical Engineering Journal, 2020, 380:122568.

[14]	Ji H, Xu Y, Shi H, et al. Enhanced activation of persulfate by magnetic NiFe₂O₄@CuO coupled with ultrasonic for degradation of oxytetracycline:Activation mechanism and degradation pathway[J]. Applied Surface Science, 2024, 652:159373.

[15]	Yao J, Liu J, Wei Z, et al. Performance and mechanism of natural chalcopyrite for photocatalytic activation of peroxymonosulfate towards tetracycline degradation[J]. Materials Research Bulletin, 2023, 164:112275.

[16]	周书葵, 田瑞, 段毅, 等. CuO/CoFe₂O₄活化过一硫酸盐去除四环素的研究[J]. 现代化工, 2022, 42(9):102-108.

[17]	Guo S, Wang H, Yang W, et al. Scalable synthesis of Ca-doped α-Fe₂O₃ with abundant oxygen vacancies for enhanced degradation of organic pollutants through peroxymonosulfate activation[J]. Applied Catalysis B:Environmental, 2020, 262:118250.

[18]	Ren W, Nie G, Zhou P, et al. The intrinsic nature of persulfate activation and N-doping in carbocatalysis[J]. Environmental Science & Technology, 2020, 54(10):6438-6447.

[19]	Zhang T, Yang Y, Li X, et al. Degradation of sulfamethazine by persulfate activated with nanosized zero-valent copper in combination with ultrasonic irradiation[J]. Separation and Purification Technology, 2020, 239:116537.

[20]	Deng J, Xu M, Chen Y, et al. Highly-efficient removal of norfloxacin with nanoscale zero-valent copper activated persulfate at mild temperature[J]. Chemical Engineering Journal, 2019, 366:491-503.

[21]	Jawad A, Zhan K, Wang H, et al. Tuning of persulfate activation from a free radical to a nonradical pathway through the incorporation of non-redox magnesium oxide[J]. Environmental Science & Technology, 2020, 54(4):2476-2488.

[22]	Liu T, Yin K, Li N, et al. Efficient activation of peroxymonosulfate by copper supported on polyurethane foam for contaminant degradation:Synergistic effect and mechanism[J]. Chemical Engineering Journal, 2022, 427:131741.

[23]	任富彦. Bi₂O₃/g-C₃N₄-Nd复合光催化剂的制备及其光催化性能研究[J]. 现代化工, 2025, 45(3):160-165,171.

[24]	Guo S, Li C, You L, et al. Facile synthesis of AgFeO₂-decorated CaCO₃ with enhanced catalytic activity in activation of peroxymonosulfate for efficient degradation of organic pollutants[J]. Advanced Energy and Sustainability Research, 2021, 2(8):2100038.

[25]	Wang B, He D, Zhu D, et al. Electron-rich ketone-based covalent organic frameworks supported nickel oxyhydroxide for highly efficient peroxymonosulfate activation and sulfadiazine removal:Performance and multi-path reaction mechanisms[J]. Separation and Purification Technology, 2022, 296:121350.

[26]	Xiao C, Zhang M, Wang C, et al. 2D metal-organic framework derived hollow Co/NC carbon sheets for peroxymonosulfate activation[J]. Chemical Engineering Journal, 2022, 444:136385.