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Article(id=1241406720598135526, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.06.032, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717171200000, receivedDateStr=2024-06-01, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773904026412, onlineDateStr=2026-03-19, pubDate=1732982400000, pubDateStr=2024-12-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773904026412, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773904026412, creator=13701087609, updateTime=1773904026412, updator=13701087609, issue=Issue{id=1241406711219680205, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='6', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773904024176, creator=13701087609, updateTime=1773911273793, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241437118384362345, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241437118388556650, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241406711219680205, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=151, endPage=155, ext={EN=ArticleExt(id=1241406720921096952, articleId=1241406720598135526, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Preparation and Photocatalytic Performance of TiO2-CNTs Composite Photocatalyst, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

A composite photocatalyst of TiO2-CNTs was synthesized by adopting the sol-gel method and ultrasonic dispersion, and then its activity in the photocatalytic reduction of CO2 was tested. With a load capacity of carbon nanotubes (CNTs) at 0.75%, the TiO2-CNTs present a better performance in photocatalytic CO2 reduction. Under UV irradiation with wavelength of 365 nm, the average yield of CH4 and CO from the composite catalyst are enhanced by 90% and 156% respectively, compared to the usage of single TiO2 catalyst. It is believed that the reaction is based on the following mechanisms: CNTs, as a co-catalyst, forms a compact electron transport structure with semiconductor of TiO2, which significantly accelerates the transfer of photogenic carriers and reduces the electron-cave recombination efficiency. In addition, high specific surface area and excellent adsorption performance of CNTs can increase active sites for reaction, thus improving efficiency of photocatalytic reduction of CO2 by the catalyst.

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采用溶胶-凝胶法和超声分散法制备了TiO2-CNTs复合光催化剂，并进行了光催化还原CO2活性测试。结果表明，当CNTs负载量为0.75%时，TiO2-CNTs复合光催化剂光催化还原CO2的性能较佳，在波长365 nm的紫外光照射下，相比于单一TiO2催化剂，CH4平均产率提升了90%，CO平均产率提升了156%。反应机理认为：CNTs作为助催化剂与半导体TiO2形成了紧密的电子传输结构，显著加快了光生载流子的转移，降低了电子-空穴的复合效率；此外，CNTs高比表面积和优异的吸附性能可以增加反应活性位点，从而提高催化剂光催化还原CO2效率。

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张瀚文（1995—），男，黑龙江大庆人，硕士研究生，主要研究方向为光催化还原CO2。E-mail：

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张瀚文（1995—），男，黑龙江大庆人，硕士研究生，主要研究方向为光催化还原CO2。E-mail：

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张瀚文（1995—），男，黑龙江大庆人，硕士研究生，主要研究方向为光催化还原CO2。E-mail：

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journalId=1235980550691926019, articleId=1241406720598135526, language=CN, label=图9, caption=紫外光下光催化还原CO2活性测试结果

（a）TiO2-CNTs复合光催化剂的平均产率；（b）紫外光下TiO2和TiO2-0.75%CNTs产率对比

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样品名称比表面积/（m2·g-1）
TiO2-0.05%CNTs5.493
TiO2-0.25%CNTs8.332
TiO2-0.50%CNTs16.470
TiO2-0.75%CNTs21.030
TiO2-1.00%CNTs25.840
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不同TiO2-CNTs复合光催化剂的比表面积

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样品名称比表面积/（m2·g-1）
TiO2-0.05%CNTs5.493
TiO2-0.25%CNTs8.332
TiO2-0.50%CNTs16.470
TiO2-0.75%CNTs21.030
TiO2-1.00%CNTs25.840
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TiO2-CNTs复合光催化剂的制备及其光催化性能
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张瀚文 1 , 习小明 1 , 卓晓军 1 , 沈裕军 1 , 周小舟 2 , 彭俊 1
矿冶工程杂志 | 材料 2024,44(6): 151-155
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矿冶工程杂志 | 材料 2024, 44(6): 151-155
TiO2-CNTs复合光催化剂的制备及其光催化性能
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张瀚文1 , 习小明1, 卓晓军1, 沈裕军1, 周小舟2, 彭俊1
作者信息
  • 1.长沙矿冶研究院有限责任公司，湖南　长沙　410012
  • 2.中南大学　冶金与环境工程学院，湖南　长沙　410083

    • 张瀚文（1995—），男，黑龙江大庆人，硕士研究生，主要研究方向为光催化还原CO2。E-mail：

Preparation and Photocatalytic Performance of TiO2-CNTs Composite Photocatalyst
Hanwen ZHANG1 , Xiaoming XI1, Xiaojun ZHUO1, Yujun SHEN1, Xiaozhou ZHOU2, Jun PENG1
Affiliations
  • 1.Changsha Research Institute of Mining and Metallurgy Co., Ltd., Changsha 410012, Hunan, China
  • 2.School of Metallurgy and Environmental Engineering, Central South University, Changsha 410083, Hunan, China
出版时间: 2024-12-01 doi: 10.3969/j.issn.0253-6099.2024.06.032
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摘要
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采用溶胶-凝胶法和超声分散法制备了TiO2-CNTs复合光催化剂，并进行了光催化还原CO2活性测试。结果表明，当CNTs负载量为0.75%时，TiO2-CNTs复合光催化剂光催化还原CO2的性能较佳，在波长365 nm的紫外光照射下，相比于单一TiO2催化剂，CH4平均产率提升了90%，CO平均产率提升了156%。反应机理认为：CNTs作为助催化剂与半导体TiO2形成了紧密的电子传输结构，显著加快了光生载流子的转移，降低了电子-空穴的复合效率；此外，CNTs高比表面积和优异的吸附性能可以增加反应活性位点，从而提高催化剂光催化还原CO2效率。

光催化剂  /  二氧化碳  /  碳纳米管  /  TiO2  /  溶胶-凝胶法  /  紫外光  /  催化还原  /  活性点位  /  光生载流子

A composite photocatalyst of TiO2-CNTs was synthesized by adopting the sol-gel method and ultrasonic dispersion, and then its activity in the photocatalytic reduction of CO2 was tested. With a load capacity of carbon nanotubes (CNTs) at 0.75%, the TiO2-CNTs present a better performance in photocatalytic CO2 reduction. Under UV irradiation with wavelength of 365 nm, the average yield of CH4 and CO from the composite catalyst are enhanced by 90% and 156% respectively, compared to the usage of single TiO2 catalyst. It is believed that the reaction is based on the following mechanisms: CNTs, as a co-catalyst, forms a compact electron transport structure with semiconductor of TiO2, which significantly accelerates the transfer of photogenic carriers and reduces the electron-cave recombination efficiency. In addition, high specific surface area and excellent adsorption performance of CNTs can increase active sites for reaction, thus improving efficiency of photocatalytic reduction of CO2 by the catalyst.

photocatalyst  /  CO2  /  carbon nanotube  /  TiO2  /  sol-gel method  /  UV light  /  catalytic reduction  /  active site  /  photogenic carrier
张瀚文, 习小明, 卓晓军, 沈裕军, 周小舟, 彭俊. TiO2-CNTs复合光催化剂的制备及其光催化性能. 矿冶工程杂志, 2024 , 44 (6) : 151 -155 . DOI: 10.3969/j.issn.0253-6099.2024.06.032
Hanwen ZHANG, Xiaoming XI, Xiaojun ZHUO, Yujun SHEN, Xiaozhou ZHOU, Jun PENG. Preparation and Photocatalytic Performance of TiO2-CNTs Composite Photocatalyst[J]. Mining and Metallurgical Engineering, 2024 , 44 (6) : 151 -155 . DOI: 10.3969/j.issn.0253-6099.2024.06.032
正文
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能源短缺危机加速了人类开发可再生清洁能源的进度。有研究表明，太阳能转化效率10%时，利用地球陆地面积0.16%的太阳能可产生约20 TW的能量，这大约是全球化石燃料能量的2倍[1]。因此，开发能够收集和转化太阳能的能源技术已成为科研热点[2]。
自1979年Inoue等[3]首次利用CdS、TiO2和WO3等半导体材料成功实现CO2光催化还原以来，光催化技术因其能够将光能转化为化学能而受到广泛关注。光催化还原CO2能够将CO2转化为有用资源，缓解全球变暖和能源危机[4]。
TiO2因其成本低廉、无毒性、在水环境中高稳定性，以及易于制备成纳米级颗粒等优点，成为目前研究最多的粉末光催化系统半导体材料[5-6]。然而，单一TiO2光催化剂存在一些局限性，如带隙宽度较大、表面反应活性位点不足以及光生电子-空穴对的快速复合，这些因素均限制了其光催化还原CO2的效率[7-8]。
碳材料以其优异的导电性、高比表面积和低费米能级，被视为一种优良的改性剂，能够显著提升光催化剂的性能[9]。本文结合溶胶-凝胶法和超声分散法制备TiO2-CNTs复合光催化剂，并分析了其在弱紫外光（365 nm）下光催化还原CO2的性能。
1　TiO2-CNTs复合光催化剂实验
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1.1　实验试剂和设备
实验试剂主要包括钛酸四丁酯（C16H36O4Ti）、冰醋酸（C2H4O2）、无水乙醇（C2H6O）、硝酸（HNO3），试剂均为分析纯，使用前未经进一步纯化。碳纳米管（CNTs）购自苏州碳丰石墨烯科技有限公司，纯度95%，直径8～15 nm、长度3～12 μm。实验用水为去离子水。
实验设备主要包括马弗炉、恒温干燥箱、气相色谱仪、磁力搅拌器、Labsolar 6A全自动微量气体分析系统等。
1.2　实验原理和方法
采用溶胶-凝胶法制备TiO2-CNTs复合光催化剂，在溶胶中超声分散碳纳米管以保证复合材料结构的均匀性。当照射到TiO2的光子能量大于带隙时，电子被激发至导带形成电子-空穴对。具有强氧化能力的空穴将水氧化，电子则参与CO2还原反应。由于碳纳米管和半导体的费米能级和逸出功不同，光生电子会由逸出功较低的半导体流向逸出功较高的碳纳米管，从而促进光生电子和空穴的分离，进而提升材料的光催化性能。
采用X射线衍射（XRD）分析样品晶体结构；采用透射电子显微镜（TEM）观察催化剂表面形貌和结构；采用热重分析（TG）确定助催化剂负载量和热性能；通过BET比表面积测试法分析样品比表面积和吸附性能；采用紫外-可见光分光光度计分析样品光学性质和能带结构；应用拉曼光谱对比负载助催化剂前后化学键和官能团情况；通过电化学工作站，利用电化学阻抗谱（EIS）研究催化剂光生电荷转移阻力，利用光电流响应测试分析载流子分离效率。
1.3　TiO2-CNTs的制备
取10 mL钛酸四丁酯溶解于34 mL无水乙醇中并加入2.6 mL冰醋酸进行充分搅拌，记作混合液A，混合时有白色沉淀生成并迅速溶解；将14 mL无水乙醇和1.6 mL去离子水充分混合，记作混合液B；通过蠕动泵将混合液B滴加至混合液A中并充分搅拌，记作混合液C，滴加速度为2 mL/min，通过浓硝酸调节混合液C的pH值至3左右，根据溶液中钛元素物质的量加入不同物质的量碳元素的碳纳米管进行负载，碳元素物质的量是钛元素的0.1、0.5、1.0、1.5、2.0倍，换算成质量（质量分数）分别是0.033 4 g（0.05%）、0.167 g（0.25%）、0.334 g（0.50%）、0.501 g（0.75%）、0.668 g（1.00%）。充分搅拌4 h后超声处理30 min，得到黑色TiO2-CNTs混合溶胶。将TiO2-CNTs混合溶胶用保鲜膜密封，在30 ℃下老化3 d，得到黑色果冻状TiO2-CNTs凝胶。然后，将TiO2-CNTs凝胶放入100 ℃恒温干燥箱中烘干，在马弗炉中650 ℃下退火，升温速度10 ℃/min，保温2 h。所得材料冷却后球磨并过200目（75 μm）筛，即得到不同碳纳米管负载量的TiO2-CNTs复合光催化剂。
1.4　光催化还原CO2活性测试
采用功率为300 W的PLS-SXE300/300UV型氙灯作为光源，通过加盖365 nm的透光片进行紫外光照射，电流15 A，从反应器的石英玻璃窗口垂直照射，完全覆盖催化剂放置范围，光源距离反应容器底部12 cm。
采用循环冷却水保持反应温度为10 ℃，搅拌速度为300 r/min，反应容器为圆柱体，底部直径8 cm。实验取0.5 g NaOH和1.58 g Na2SO3固体配制成水溶液，用250 mL容量瓶定容得到浓度为0.05 mol/L的NaOH和Na2SO3混合溶液。取80 mL混合溶液放入反应容器中，称取200 mg TiO2-CNTs复合光催化剂，充分搅拌30 min。反应器抽真空后，缓慢向容器注入体积分数99.999%的CO2至压力为80 kPa，确保系统达到气液平衡。重复操作2次确保没有空气残留，打开光源，反应10 h。采用FUL9790Ⅱ型气相色谱仪检测材料的气体产物，设置Labsolar 6A全自动进样系统自动进样，每2 h测试一次。光催化还原CO2系统如图1所示。
2　实验结果与讨论
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2.1　热重分析（TG）
图2为负载0.334 g碳纳米管（CNTs质量分数0.50%）的TiO2-CNTs复合光催化剂在空气气氛下的热重分析（TG）和微分热重（DTG）曲线。
从图2可以看出，30～400 ℃范围内，随着温度升高，TiO2-CNTs材料质量呈缓慢下降趋势，这是材料中水分蒸发和有机杂质碳化所致；400～550 ℃时，材料质量保持稳定，没有发生明显变化，表明在此温度范围内材料中水分和有机杂质已经基本挥发完毕；550 ℃时，发生有机杂质碳的氧化，质量缓慢下降，650 ℃时基本完成氧化过程，之后材料质量趋于稳定；800 ℃左右时，碳纳米管开始迅速氧化分解，到1 000 ℃时反应结束，材料质量不再发生变化。
通过精确控制碳纳米管的负载量，可以有效调节TiO2-CNTs复合光催化剂的热稳定性和氧化行为，为进一步优化光催化剂的性能提供了重要的实验依据。
2.2　X射线衍射（XRD）分析
图3为不同碳纳米管负载量的TiO2-CNTs复合光催化剂XRD图谱。由图3可知，TiO2-CNTs材料主要包含锐钛矿相（PDF#21-1272）和金红石相（PDF#21-1276）。碳纳米管负载量较低（0.05%～0.25%）时，随着碳纳米管负载量增加，金红石相衍射峰强度逐渐减弱，表明负载碳纳米管对金红石相的形成具有抑制作用；碳纳米管负载量增至0.50%及以上时，会抑制金红石相形成，这可能是碳原子渗入晶格所致；随着碳纳米管负载量进一步提高，TiO2-CNTs材料的XRD图谱半峰宽逐渐增宽，显示出晶粒尺寸有细微减小趋势。这可能是由于CNTs促进了晶粒的细化，进而影响了材料的微观结构。
2.3　BET比表面积测试
采用氮气吸附-脱附法分析TiO2-CNTs复合光催化剂的比表面积，结果见表1。从表1可以看出，负载碳纳米管显著提升了TiO2-CNTs材料的比表面积，从而可能增强其在催化反应中的有效活性位点。
2.4　透射电子显微镜（TEM）分析
图4为TiO2-0.50%CNTs复合光催化剂的透射电子显微镜（TEM）分析结果。从图4可以看出，碳纳米管直径约为7 nm，碳纳米管周围紧密包覆着大量近球形的TiO2颗粒，这些颗粒的直径与碳纳米管相近。碳纳米管在TiO2-CNTs材料中的分布密度并不高，但与TiO2颗粒之间展现出了良好的界面结合，有助于光生载流子的有效分离和传输，从而增强整体的光催化活性。
2.5　拉曼光谱
图5为单一TiO2催化剂及TiO2-0.50%CNTs复合光催化剂的拉曼光谱。锐钛矿相TiO2催化剂的特征拉曼位移波数分别为145 cm-1、399 cm-1、515 cm-1和639 cm-1，对应于TiO2不同振动模式。经过650 ℃退火处理后，TiO2催化剂和TiO2-0.50%CNTs复合光催化剂均展现出了一致的拉曼位移波数，即142 cm-1、393 cm-1、514 cm-1和635 cm-1。其中，393 cm-1、514 cm-1和635 cm-1的峰位分别对应于TiO2的B1g、A1g和B2g的振动模式，验证了TiO2的锐钛矿结构。两种材料峰值强度上的明显变化，表明负载CNTs对TiO2化学键结构产生了影响，CNTs与TiO2之间可能形成了新的化学键或改变了原有的化学键状态。此外，TiO2-0.50%CNTs复合光催化剂的拉曼光谱在1 352 cm-1和1 592 cm-1处出现了小峰，分别对应CNTs的D模和G模振动，进一步证实了CNTs在TiO2-CNTs材料中的成功复合。
2.6　紫外-可见漫反射分析
图6为不同碳纳米管负载量对TiO2-CNTs复合光催化剂紫外-可见漫反射光谱的影响。由图6可知，相比于650 ℃退火的单一TiO2催化剂，TiO2-CNTs复合光催化剂在200～800 nm波长范围内的吸光度增强。
随着CNTs掺杂量增加，TiO2-CNTs材料的禁带宽度逐渐减小，这可能与CNTs在TiO2中的掺杂效应有关，从而促进了电子从价带到导带的跃迁，增强了材料的光催化活性。在400～600 nm的可见光区域，随着CNTs负载量增加，材料吸光度随之提高，表明负载CNTs不仅拓宽了TiO2的光吸收范围，而且显著提升了其在可见光区域的光吸收能力。
根据Kubelka-Munk函数计算TiO2-0.75%CNTs复合光催化剂禁带宽度为3.11 eV。
2.7　光电化学性能分析
为了深入研究催化剂中光生电荷的转移效率，采用电化学阻抗谱（EIS）测试TiO2-0.50%CNTs材料的光电化学性能，结果如图7所示。与单一TiO2相比，TiO2-0.50%CNTs材料在高频区域的电化学阻抗谱中展现出更小的圆弧半径，表明其具有较低的界面电荷转移电阻。这是利用了碳纳米管的高导电性，以及碳纳米管与纳米级TiO2之间的良好接触，共同优化了TiO2-CNTs材料内部的电荷转移路径。
利用光电流响应测试（I-t曲线）分析载流子的分离效率，实验利用氙灯产生的光模拟自然太阳光。如图8所示，TiO2-0.50%CNTs复合光催化剂产生的光电流强度显著高于单一TiO2，这是因为负载碳纳米管不仅增强了材料的吸光性能，而且在微观结构上改善了电荷转移路径。此外，在多次循环测试后，TiO2-0.50%CNTs材料依然展现出良好的光电流响应。综上所述，负载碳纳米管显著提升了材料中电子-空穴分离效率，增强了复合材料光催化性能。
2.8　紫外光下光催化还原CO2活性评价
紫外光下光催化还原CO2活性测试结果如图9所示。TiO2-0.75%CNTs复合光催化剂在光催化过程中产率最高，其中CO产率为102.90 nmol/（g·h），CH4产率为35.58 nmol/（g·h），CO产率超过CH4，并随着CNTs负载量增加，增幅更为显著。然而，在产物中未检测出H2，这可能是由于其产率极低或碳纳米管的疏水性影响了产物的检测。
当碳纳米管负载量为0.05%～0.75%时，光催化效果随着碳纳米管负载量增加而提升，但当碳纳米管负载量进一步增加时，产率开始下降，推测可能是过量碳纳米管对TiO2的部分活性位点的光吸收产生遮蔽作用，从而降低了催化效率。图9（b）显示，在相同的实验条件下，与单一TiO2相比，TiO2-0.75%CNTs复合光催化剂CH4平均产率提升了90%，CO平均产率提升了156%。此外，进行的空白实验中未检测到任何气体产生，进一步证实了TiO2-CNTs复合光催化剂在光催化还原CO2过程中的优越性。
TiO2-CNTs复合光催化剂的反应机理如图10所示。
与单一TiO2相比，TiO2-CNTs复合光催化剂具有较低的费米能级，促进了从TiO2激发产生的光生电子向CNTs的高效转移，进而有效地还原CO2生成燃料。当光照射到TiO2-CNTs复合材料表面时，电子从TiO2的价带（VB）激发到导带（CB），并通过C—O—Ti键转移到碳纳米管上。这一过程不仅促进了电子的传输，也抑制了电子-空穴对的复合，从而增强了光催化活性。
在CNTs上，光生电子可以在众多活性位点上参与还原吸附的CO2分子，生成CO2-·自由基。随后，CO2-·被进一步氧化为CO，并在碳纳米管表面与吸附的H·相互作用生成C·自由基，最终，通过一系列的氧化还原反应，C·自由基与H·自由基结合生成CH4。而TiO2价带的空穴也传递到半导体表面，把H2O氧化为OH·和H+。生成CH4比生成CO需要更多的电子，因此更为困难，这也是实验中CO产率高于CH4产率的原因。
此外，在退火过程中，部分C原子可能渗入TiO2晶格之中，不仅影响了金红石相的形成，还可能通过C—O键在TiO2的导带和价带之间形成新的能带[10]，导致材料吸收带边的红移，从而拓宽了材料对光的响应范围，增加了可见光区域的光吸收能力。
3　结论
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1）采用溶胶-凝胶法制备了TiO2-CNTs复合光催化剂，TiO2-0.75%CNTs复合光催化剂光催化还原CO2的产率最高，其中CO产率为102.9 nmol/（g·h），CH4产率为35.58 nmol/（g·h）。相比于单一TiO2催化剂，TiO2-CNTs复合光催化剂CO、CH4平均产率分别提升了156%和90%。
2）负载碳纳米管能扩大光响应范围，使光吸收峰红移。
3）负载碳纳米管有效降低了光生电子的传输阻力，提升了TiO2-CNTs材料的比表面积和表面活性位点数量，形成的复合结构抑制了电子-空穴对复合，这也是TiO2-CNTs材料光催化还原CO2能力提高的主要原因。
基金
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  • 南岭钨锡钼铋资源综合开发与精深加工利用集成示范(2022YFC2905105-3/5)
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参考文献 引证文献
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2024年第44卷第6期
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doi: 10.3969/j.issn.0253-6099.2024.06.032
  • 接收时间：2024-06-01
  • 首发时间：2026-03-19
  • 出版时间：2024-12-01
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  • 收稿日期：2024-06-01
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南岭钨锡钼铋资源综合开发与精深加工利用集成示范(2022YFC2905105-3/5)
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    1.长沙矿冶研究院有限责任公司，湖南　长沙　410012
    2.中南大学　冶金与环境工程学院，湖南　长沙　410083
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2种不同金属材料的力学参数
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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