现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (1) : 131-136. DOI: 10.16606/j.cnki.issn0253-4320.2025.01.024

科研与开发

碳材料表面活性基团对苯甲醇氧化催化性能的调控研究

陈志佳 ¹ ,
王盛 ¹ ,
杨本群 ²^,^* ,
杨慧敏 ¹^,^*

作者信息 +

Modulation of surface active groups of carbon material on its performance in catalytic oxidation of benzyl alcohol

CHEN Zhi-jia ¹ ,
WANG Sheng ¹ ,
YANG Ben-qun ²^,^* ,
YANG Hui-min ¹^,^*

Author information +

文章历史 +

Received		Published
2024-03-12		2025-01-20
Issue Date	Revised Date
2025-01-17	2024-03-12

PDF (4635K)

摘要

采用硝酸对生物质基活性炭进行改性处理引入含氧基团(SOGs),研究了碳材料表面官能团对催化苯甲醇氧化反应性能的调控作用。通过SEM、XRD、XPS等对制备的催化剂进行表征,考察了硝酸浓度对活性炭表面氧化基团的影响。结果表明,当用浓度为1.5 mol/L的HNO₃处理活性炭时,煅烧后所得催化剂AC-1.5催化苯甲醇氧化反应的转化率为94%,选择性为99%,使用5次后仍保持活性,这主要与AC-1.5中羰基含量高有直接关系。该研究结果为开发高效、低成本的生物质基催化剂提供参考。

Abstract

Biomass-based activated carbon is added with surface oxygen-containing groups (SOGs) through being modified by nitric acid,and the modulation of surface functional groups of carbon material on the performance of the catalyst for catalytic oxidation reaction of benzyl alcohol is investigated.The prepared catalyst is characterized by means of SEM,XRD,XPS and other measurements,and the influence of the concentration of nitric acid on the level of SOGs on activated carbon is studied.It is found that the conversion of benzyl alcohol reaches 94% and the selectivity is 99% when the AC-1.5 catalyst,which is obtained through treating the activated carbon with HNO₃ at a concentration of 1.5 mol·L^-1,and then calcined,is served as the catalyst.The AC-1.5 catalyst can maintain its activity after it has been used for five times at least.This is mainly due to the high carbonyl content in AC-1.5.This study result can provide a reference for the development of efficient and low-cost biomass-based catalysts.

Graphical abstract

关键词

活性炭 / 催化氧化 / 羰基 / 含氧基团

Key words

activated carbon / catalytic oxidation / carbonyl group / oxygen-containing groups

Author summay

陈志佳(1999-),男,硕士生,主要研究方向为多相催化,2579777804@qq.com。

引用本文

引用格式 ▾

[Author(id=1241353042424984273, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=2579777804@qq.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1241353042450150099, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042424984273, language=EN, stringName=Zhi-jia CHEN, firstName=Zhi-jia, middleName=null, lastName=CHEN, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹, address=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241353042475315924, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042424984273, language=CN, stringName=陈志佳, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹, address=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000, bio={"content":"

陈志佳(1999-),男,硕士生,主要研究方向为多相催化,2579777804@qq.com。

"}, bioImg=null, bioContent=

陈志佳(1999-),男,硕士生,主要研究方向为多相催化,2579777804@qq.com。

, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241353042362069706, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, xref=null, ext=[AuthorCompanyExt(id=1241353042366264011, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China), AuthorCompanyExt(id=1241353042370458316, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000)])]), Author(id=1241353042496287446, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, 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=1241353042521453272, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042496287446, language=EN, stringName=Sheng WANG, firstName=Sheng, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹, address=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241353042542424793, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042496287446, language=CN, stringName=王盛, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹, address=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241353042362069706, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, xref=null, ext=[AuthorCompanyExt(id=1241353042366264011, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China), AuthorCompanyExt(id=1241353042370458316, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000)])]), Author(id=1241353042563396315, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, orderNo=2, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=yangbenqunlicp2009@163.com, emailSecond=null, emailThird=null, correspondingAuthor=1, authorType=1, ext={EN=AuthorExt(id=1241353042588562141, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042563396315, language=EN, stringName=Ben-qun YANG, firstName=Ben-qun, middleName=null, lastName=YANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=²^,^*, address=2. College of Chemical Engineering and Technology, Tianshui Normal University, Tianshui 741000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241353042613727966, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042563396315, language=CN, stringName=杨本群, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=²^,^*, address=2.天水师范学院化学工程与技术学院,甘肃天水 741000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241353042391429837, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, xref=null, ext=[AuthorCompanyExt(id=1241353042395624142, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042391429837, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2. College of Chemical Engineering and Technology, Tianshui Normal University, Tianshui 741000, China), AuthorCompanyExt(id=1241353042399818447, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042391429837, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.天水师范学院化学工程与技术学院,甘肃天水 741000)])]), Author(id=1241353042634699488, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, orderNo=3, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=emma920@imust.edu.cn, emailSecond=null, emailThird=null, correspondingAuthor=1, authorType=1, ext={EN=AuthorExt(id=1241353042655671010, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042634699488, language=EN, stringName=Hui-min YANG, firstName=Hui-min, middleName=null, lastName=YANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹^,^*, address=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241353042680836835, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, authorId=1241353042634699488, language=CN, stringName=杨慧敏, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=¹^,^*, address=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1241353042362069706, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, xref=null, ext=[AuthorCompanyExt(id=1241353042366264011, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014000, China), AuthorCompanyExt(id=1241353042370458316, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240719913691607791, companyId=1241353042362069706, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.内蒙古科技大学化学与化工学院,内蒙古包头 014000)])])] 陈志佳,王盛,杨本群,杨慧敏. 碳材料表面活性基团对苯甲醇氧化催化性能的调控研究[J]. 现代化工, 2025, 45(1): 131-136 DOI:10.16606/j.cnki.issn0253-4320.2025.01.024

登录浏览全文

4963

注册一个新账户忘记密码

苯甲醇氧化生成的苯甲醛是一种通用的合成具有高附加值精细化学品的中间体^[1-2],广泛应用于制药、染料、食品、化妆品和农业化学工业中^[3⇓-5]。传统催化苯甲醇氧化需要使用危险且昂贵的无机盐作氧化剂,如次氯酸盐、氧化锰、高锰酸盐、氧化铬和重铬酸盐。从环境友好和原子经济的角度出发,温和条件下采用空气或分子氧选择性氧化苯甲醇是更优的选择。虽然Ru、Au、Pt、和Pd等贵金属基催化剂在温和条件下用于苯甲醇氧化反应获得了优异的催化性能^[6⇓-8],但其昂贵的成本阻碍了其商业化应用。而Mn、Ni和Co等非贵金属基催化剂也存在金属浸出、稳定性差、环境污染等缺点^[9⇓-11],限制了其在制药和生物医学领域的应用。因此,需要探索具有高催化效率的无金属催化体系来选择性氧化苯甲醇制苯甲醛。

由于碳材料具有比表面积大、机械化学稳定性高、耐酸碱能力强及表面易改性等特点,其直接作为催化剂而广泛用于多相催化体系中。碳材料种类非常丰富,包括金刚石、富勒烯、纳米锥、石墨炔、碳纳米管、碳纳米纤维、石墨烯和碳气凝胶等。研究表明,由于碳材料具有丰富的表面官能团,使其在脱氢、氧化和加氢反应中表现出活性^[12]。近年来,无机碳材料在烷烃和醇氧化研究中取得了很好的进展。Long等^[13]报道了掺杂氮杂原子的多层石墨烯纳米片可以有效地催化伯醇的有氧选择性氧化。氧分子能被N-石墨烯激活,形成sp² N-O₂加合过渡态,可以将醇氧化成醛。Xiao等^[14]研究无金属功能化氧化石墨烯(GO)在空气中氧化环己烷显示出较高的催化性能。研究发现氧化石墨烯薄片表面的羧酸基团是将O₂转化为·

O 2 -

的活性位点。

活性炭(AC)虽然被广泛用作载体,但很少有文献报道使用活性炭直接作催化剂,与其他碳纳米催化剂相比,其催化活性较差。其中,孔隙连通性差和体积形态差是其催化反应活性差的主要原因之一,主要是由于这种结构不利于催化剂与反应物分子之间的传质和扩散。活性炭表面官能团的种类和密度可以通过适当的化学或热处理方法来调整。将活性炭在气相或液相中经氧化处理,则可以在活性炭表面引入羧基、酚羟基、内酯和醌等酸性基团^[15]。丰富的表面官能团有利于其催化活性的提高^[16]。在苯甲醇氧化过程中,Zhu等^[17]提出活性炭的表面含氧基团参与了氧的活化过程。Andreoli等^[18]通过软模板方法合成具有调谐表面功能的有序介孔碳材料,其在苯甲醇氧化制苯甲醛过程中进行了测试,证明表面上存在更多的醌和羰基对无金属碳基催化剂催化性能的影响。因此,碳材料的表面改性对催化性能有很大的影响。为了获得满意的催化剂,通常需要对碳载体进行氧化(用HNO₃、KMnO₄等)来生成含氧基团^[19]。硝酸是最常用的碳纳米管氧化试剂,其可以选择性地去除无定形碳和金属杂元素,同时在暴露的碳纳米管表面产生丰富的含氧基团^[20]。

笔者系统研究了硝酸浓度对活性炭表面官能团的影响,以苯甲醇催化氧化反应为模板反应,探究其表面结构与催化性能之间的关系。通过SEM、XPS、BET等分析手段对制备的催化剂进行表征,考察了硝酸浓度和温度对活性炭载体表面氧基团的影响。

1 材料试剂与仪器

1.1 材料与试剂

活性炭(AC),国药集团化学试剂有限公司生产;硝酸,天津北联精细化学试剂有限公司生产;苯甲醇、苯甲醛,国药集团化学试剂有限公司生产;氢氧化钾、联苯及底物,上海阿拉丁生化科技股份有限公司生产。所有化学品均为分析纯,无需纯化处理。

1.2 仪器

GC 9790plus气相色谱仪,浙江福立分析仪器有限公司生产。

2 实验方法

2.1 硝酸修饰活性炭催化剂的制备

选择一种由椰子壳制成的市售活性碳(AC)作催化剂。称取2 g活性炭,用50 mL浓度为1.5 mol/L HNO₃溶液在80℃下预处理6 h,以引入含氧基团,然后离心洗涤至中性,在100℃下干燥12 h。最后将得到的AC样品在400℃下煅烧3 h。所得到的黑色粉末命名为AC-1.5。当硝酸的浓度分别为1、2、3 mol/L时,催化剂被命名AC-1、AC-2和AC-3。未活化的催化剂命名为AC。

2.2 苯甲醇氧化测试

首先将0.5 mmol苯甲醇置于反应管中,分别加入0.2 mmol KOH、0.05 g催化剂及2 mL溶剂。用氧气吹扫1 min,彻底消除空气后,将带有注射器针头的充氧球囊插入其中。通入氧气密封后将其置于恒温磁力搅拌器上,在100℃下反应12 h,反应降至室温后加入0.05 mmol联苯作标准物,稀释后用气相色谱仪进行分析,色谱柱为KB-1,检测器为FID。

2.3 循环实验

每次实验结束后分离出的催化剂用无水乙醇和水溶液洗涤数次并离心过滤,在80℃烘箱下干燥12 h后将其用于下一轮实验中。

3 结果与分析

3.1 形貌与结构表征

3.1.1 SEM表征

为了探究其结构与性能的关系,利用SEM对AC的形貌结构进行了研究。样品的SEM图及对应的C和O元素mapping图如图1所示。

从图1(a)中可以看出,未处理的AC表面光滑。从图1(b)、图1(c)中可以看出,硝酸氧化后AC表面微结构出现明显的侵蚀和瓦解现象,形成了大量细小颗粒。从图1(d)、图1(e)中可以看出,随着硝酸浓度的进一步增大,这种侵蚀现象越严重,结果会造成活性炭中微孔的变形或相邻微孔之间的合并,从而导致活性炭中产生大量的大孔结构^[21]。经过硝酸处理后得到的大孔结构则起到一定的物质传输作用,从而促进物质在催化剂内部的流动,因此,经过处理后的催化剂,其催化效率都有所提高^[22]。从图1(f)中可以看出,AC-1.5催化剂表面的O元素分布较均匀。

3.1.2 XRD及拉曼光谱分析

各样品的XRD图和拉曼光谱图如图2所示。

从图2(a)中可以看出,所有样品均在2θ=24°处有1个宽衍射峰(002),在2θ=43°处对应的是石墨(001)晶面的特征衍射峰,这是明显的无定形碳的晶面的特征衍射峰^[23]。但在2θ=26°出现了部分石墨相的峰,说明碳材料存在部分石墨化^[24]。活性炭随着加热时形成部分石墨化结构,石墨化程度主要由热处理工艺的温度决定。通过拉曼光谱检测表面改性后碳材料的缺陷程度。从图3(b)中可以看出,大约在1 339 cm^-1和1 592 cm^-1处有2个明显的特征峰,分别属于无序碳(D波段)和石墨碳(G波段)^[25]。通常用I_D/I_G值来表示碳材料的缺陷。AC-1的I_D/I_G值(I_D/I_G=1.06)高于未处理的AC(I_D/I_G=1.02)。而AC-1.5的I_D/I_G值达到1.14,大大高于AC-1(I_D/I_G=1.06)、AC-2(I_D/I_G=1.03)和AC-3(I_D/I_G=1.02),说明经适当硝酸氧化可以增加碳材料的无序程度,导致催化剂形成更多的结构缺陷。

3.1.3 XPS分析

各样品的XPS全光谱、C 1s光谱和O 1s光谱如图3所示。

从图3(a)中可以看出,在285 eV和532 eV处出现2个尖峰,对应于C 1s和O 1s结合能^[26]。从图3(b)中可以看出,C 1s高分辨谱图可被解卷积成4种特征峰,分别为C—C键(284.7 eV)、C—OH键(286.4 eV)、C—O—C键(287.4 eV)和O—C=O键(289.1 eV)^[27]。从图3(c)中可以看出,O 1s高分辨谱图可被解卷积成4种特征峰:羧基(534.4 eV)、酸酐和酯中的醚氧原子(533.5 eV)、羟基上氧原子(532.5)和羰基(531.1 eV)^[28]。不同AC样品的 O 1s数据如表1所示。从表1中可以看出,AC经过硝酸氧化后C/O比例均减少,说明经过处理后样品表面含氧官能团总体数量都有所增加。其中,催化剂AC-1.5的羰基占比高达50%,比其他催化剂的都高。Zhou等^[29]曾报道高羰基占比有利于苯甲醇氧化反应的进行,说明表面羰基含量是影响催化剂活性的重要原因之一。

3.2 催化性能评价

苯甲醇氧化制苯甲醛作为一种典型的连续氧化反应,是研究好氧选择性氧化催化剂性能的经典反应。合成的一系列碳材料的催化活性及助催化剂碱量的优化结果如表2所示。

从表2中可以看出,对比未处理的AC,硝酸活化后的催化剂的转化率都有所增加,但AC-3的转化率变化不大,选择性提高的也不明显。当硝酸浓度为1.5 mmol/L时,其转化率达到最大,选择性能达到99%以上(列1—5)。随着KOH物质的量的增加,苯甲醇的转化率增加,而苯甲醛的选择性变化则相反(列6—9)。说明碱的促进作用非常明显,但是过量的碱对反应不利,主要是由于较高的碱用量会使反应进一步氧化成苯甲酸,从而降低了反应的选择性。另外,考察了碱的种类对反应的影响,结果发现,钾盐的表现最好(列10—12)。碱空白和催化剂空白实验结果进一步说明,催化剂的加入能保持反应的高选择性(列13—14)。

对催化反应条件进行进一步优化,结果如图4所示。

从图4(a)中可以看出,当催化剂质量增加至50 mg,苯甲醇的转化率显著增加,继续增加催化剂的质量,其转化率提高不明显。从图4(b)中可以看出,随着温度的升高,苯甲醇的转化率一直升高,而选择性在100℃时最大。从图4(c)中可以看出,BA在前3 h内被迅速消耗,转化率高达79.5%。随着反应时间的增加,苯甲醇的转化率继续增加,但12 h后其苯甲醛选择性下降。这是因为长时间的反应会使苯甲醛进一步氧化成苯甲酸^[30]。另外,考察了溶剂对苯甲醇氧化活性的影响。其中,甲苯作溶剂时其反应活性最高。

在优化后的反应条件下,AC-1.5在不同醇作为底物时的通用性如表3所示。

从表3中可以看出,AC-1.5催化剂对醇类的好氧氧化反应具有良好的转化率和选择性。AC-1.5催化剂对邻取代苯甲醇的催化活性低于对取代苯甲醇,这归因于位阻(列1—9)。该催化剂在氧化糠醇、对羟基苯甲醇、2-呋喃苯甲醇和3-吡啶苯甲醇方面也表现出优异的性能(列10—13),说明该催化剂醇催化氧化具有较好普适性。

对甲醇有氧氧化催化剂的可重复使用性进行了评价,结果如图5所示。

从图5中可以看出,催化剂重复使用5次后,苯甲醇的转化率在90%~93%之间,选择性有所下降,但也一直在90%以上,说明该催化剂具有良好的重现性和稳定性。

4 结论

通过硝酸氧化的方法调控活性炭表面的含氧基团,制备出的催化剂对苯甲醇氧化制苯甲醛有较好的活性。通过对材料的形貌和结构进行表征发现,通过硝酸氧化不但使材料的缺陷度增加,同时有效地调节了活性炭的表面含氧基团的水平。其中,催化剂AC-1.5表面羰基占比高达50%,这有利于苯甲醇氧化反应活性的提高。通过对反应条件的优化,AC-1.5催化苯甲醇氧化的转化率为94%,而苯甲醛选择性可达99%。另外,在底物扩展证明其有良好普适性。5次循环反应中其转化率和选择性的变化不明显,说明该催化剂的稳定性良好。该研究结果对于开发高效、低成本的生物质基催化剂具有重要意义。

参考文献

原文顺序 | 出版日期 | 本文引用

[1]	Krogul-Sobczak A, Pisarek N, Cieciorski P, et al. Silver nanoparticles densely grafted with nitroxides as a recyclable green catalyst in the selective oxidation of alcohols[J]. Nanomaterials, 2022, 12(15):57-64.

[2]	Zhang C, Huang T, Liang J, et al. A COF template-derived mesoporous CeO₂-supported Au nanoparticles catalyst for the oxidative esterification of benzaldehydes and benzyl alcohols[J]. Dalton Transations, 2023, 52(43):15907-15917.

[3]	Smyth P, Gibson T J, Irvine G, et al. pH-Responsive benzaldehyde-functionalized PEG-based polymeric nanoparticles for drug delivery:Effect of preparation method on morphology,dye encapsulation and attachment[J]. European Polymer Journal, 2020,124:109471-109471.

[4]	Wang X, Zhu B, Dong J, et al. Visible-light-mediated multicomponent reaction for secondary amine synthesis[J]. Chemical Communications, 2021, 57(41):5028-5031.

[5]	Pereira-da-Silva J, Nunes A, Mendes M, et al. Boroxine benzaldehyde complex for pharmaceutical applications probed by electron interactions[J]. Rapid Communications In Mass Spectrometry, 2023, 37(1):e9418-e9418.

[6]	Ni C, Chevalier M, Veinot JGC. Metal nanoparticle-decorated germanane for selective photocatalytic aerobic oxidation of benzyl alcohol[J]. Nanoscale Advances, 2022, 5(1):228-236.

[7]	Bera S, Banerjee F, Samanta S K. A phosphate-based organic polymer nanocontainer efficiently hosts Ag/Ru nanoparticles for heterogeneous catalytic reduction of nitroaromatics and oxidation of benzyl alcohols[J]. Chemnanomat, 2023, 9(6):e202300088.

[8]	Luo J, Yang S, Ling Y, et al. Defective Au nanoparticles manipulated by Au-Mg_xAl-LDH interplay for alkali-free oxidation of benzyl alcohol[J]. Chemical Engineering Journal, 2023,473:145171.

[9]	Li J, Zhao S, Li C, et al. Single atom manganese catalyst boosting selective oxidation of alcohols with activated peroxymonosulfate[J]. Journal of Colloid and Interface Science, 2024,656:58-67.

[10]	Xu C, Zhong S, Yuan L, et al. Insight into the promotional effect of Ce doped in (FeCoNiCrMn)₃O₄ high entropy oxides for solvent-free aerobic oxidation of benzyl alcohol[J]. Chemical Engineering Journal, 2024,481:148767.

[11]	Mirhosseyni M, Ziarani G M, Badiei A. Chitosan-derived mesoporous N-doped carbon catalyst embedded with NiO for highly selective benzyl alcohol oxidation[J]. International Journal of Biological Macromolecules, 2024,259:129093.

[12]	Ko S, Tang X, Gao F, et al. Remarkable N₂-selectivity enhancement of NH₃-SCR over HPMo modified MnCo-BTC@SiO₂ catalyst[J]. Journal of Environmental Sciences, 2024,138:482-495.

[13]	Long J, Xie X, Xu J, et al. Nitrogen-doped graphene nanosheets as metal-free catalysts for aerobic selective oxidation of benzylic alcohols[J]. ACS Catalysis, 2012, 2(4):622-631.

[14]	Xiao Y, Liu J, Xie K, et al. Aerobic oxidation of cyclohexane catalyzed by graphene oxide:Effects of surface structure and functionalization[J]. Molecular Catalysis, 2017,431:1-8.

[15]	Li Z J, Yan W F, Dai S. Surface functionalization of ordered mesoporous carbons-A comparative study[J]. Langmuir, 2005, 21(25):11999-12006.

[16]	Meng Q J, Zhang X X, Wang X C. Preparation and characterization of poly (1,3-propylene glycol-hexanedioic acid)-functionalized carbon nanotubes[J]. High Performance Polymers, 2007, 19(4):451-461.

[17]	Zhu J, Carabineiro S A C, Shan D, et al. Oxygen activation sites in gold and iron catalysts supported on carbon nitride and activated carbon[J]. Journal of Catalysis, 2010, 274(2):207-214.

[18]	Andreoli S, Benito P, Solmi M V, et al. Insights into the synthesis and surface functionalization of mesoporous carbon for catalytic applications[J]. Chemistryselect, 2017, 2(25):7590-7596.

[19]	Wen G, Diao J, Wu S, et al. Acid properties of nanocarbons and their application in oxidative dehydrogenation[J]. ACS Catalysis, 2015, 5(6):3600-3608.

[20]	Gerber I, Oubenali M, Bacsa R, et al. Theoretical and experimental studies on the carbon-nanotube surface oxidation by nitric acid:Interplay between functionalization and vacancy enlargement[J]. Chemistry-A European Journal, 2011, 17(41):11467-11477.

[21]	El-Hendawy A N A. Influence of HNO₃ oxidation on the structure and adsorptive properties of corncob-based activated carbon[J]. Carbon, 2003, 41(4):713-722.

[22]	Sekhon S S, Kaur P, Park J S. From coconut shell biomass to oxygen reduction reaction catalyst:Tuning porosity and nitrogen doping[J]. Renewable & Sustainable Energy Review, 2021,147:111173.

[23]	Luo R, Li M, Wang C, et al. Singlet oxygen-dominated non-radical oxidation process for efficient degradation of bisphenol A under high salinity condition[J]. Water Research, 2019,148:416-424.

[24]	Fechler N, Zussblatt N P, Rothe R, et al. Eutectic syntheses of graphitic carbon with high pyrazinic nitrogen content[J]. Advanced Materials, 2016, 28(6):1287-1294.

[25]	Yin Z, Liu X, Wu F, et al. Fabrication of P-doped porous carbon catalysts,with inherent N functionality,from waste peanut shells and their application in the metal-free aerobic oxidation of alcohols[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(2):911-922.

[26]	Geng L, Wu S, Zou Y, et al. Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol[J]. Journal of Colloid and Interface Science, 2014,421:71-77.

[27]	Figueiredo J L, Pereira M F R. The role of surface chemistry in catalysis with carbons[J]. Catalysis Today, 2010, 150(1/2):2-7.

[28]	Chen W, Cao J, Yang J, et al. Molecular-level insights into the electronic effects in platinum-catalyzed carbon monoxide oxidation[J]. Nature Communications, 2021, 12(1):6888-6888.

[29]	Zhou Y, Ma C, Wang X, et al. Carbonyl-anchored single-atom palladium achieved on waste printing paper-derived carbon material by impregnation method:Remarkable performance in selective oxidation of benzyl alcohol[J]. Materials Today Chemistry, 2023,28:101340.

[30]	Mao D, Qiu J, Jia M, et al. Platinum supported cellulose-based carbon with oxygen-containing functional groups for benzyl alcohol oxidation[J]. Journal of Physics and Chemistry of Solids, 2019,135:109095-109095.