Article(id=1321967871572426833, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967818057298402, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000176, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000176, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1710172800000, receivedDateStr=2024-03-12, revisedDate=null, revisedDateStr=null, acceptedDate=1714233600000, acceptedDateStr=2024-04-28, onlineDate=1793111301558, onlineDateStr=2026-10-27, pubDate=1781884800000, pubDateStr=2026-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793111301558, onlineIssueDateStr=2026-10-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793111301558, creator=13701087609, updateTime=1793111301558, updator=13701087609, issue=Issue{id=1321967818057298402, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='6', pageStart='1', pageEnd='248', issueExtLink='null', onlineDate='null', pubDate='1781884800000', pubDateStr='2026-06-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1793111288799, creator='13701087609', updateTime=1793111414358, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1321968344765411750, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967818057298402, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1321968344765411751, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321967818057298402, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=200, endPage=208, ext={EN=ArticleExt(id=1321967871790530642, articleId=1321967871572426833, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Co/N co-doped defect-rich biomass-derived porous carbon as an efficient OER/ORR bi-functional electrocatalyst, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

The development of low-cost bi-functional electrocatalysts with efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial in energy conversion and storage technologies. In this study, biomass-derived porous carbon and ZIF-67 are combined as excellent bi-functional electrocatalysts through ball milling and high-temperature pyrolysis. The effect of different pyrolysis time on the catalytic performance is investigated. It is found that the formation of Co-N-C catalyst with pyrolysis time of 3 h produces more defects,and the specific surface area is as high as 1210.01 m2·g-1. The rich microporous and mesoporous structure provides more channels for the transmission of electrolyte. In the ORR performance test,the half-wave potential can reach 0.81 V,second only to 0.85 V of the commercial Pt/C catalyst. The OER performance is 1.73 V at a current density of 10 mA·cm-2,which is better than 1.79 V of the commercial IrO2 catalyst. Further theoretical studies show that the defect-rich Co-N-C catalyst can effectively reduce the reaction barrier,and the synergistic effect of Co and N atoms promotes the ORR reaction.

, authors=Fengnan WU1, Dongao LIU1, Yufan CHEN1, Siyuan TAN1, Yinsheng WANG2, Junhe YANG1, Yuhua XUE1, Shengjuan LI1, authorsList=Fengnan WU, Dongao LIU, Yufan CHEN, Siyuan TAN, Yinsheng WANG, Junhe YANG, Yuhua XUE, Shengjuan LI, authorCompany=null, correspAuthors=Shengjuan LI, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1321967873396949093, articleId=1321967871572426833, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=Co/N共掺杂富含缺陷的生物质衍生多孔碳作为高效OER/ORR双功能电催化剂, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

开发具有高效析氧反应(OER)和氧还原反应(ORR)的低成本双功能电催化剂在能量转换和存储技术中至关重要。本工作采用球磨法和高温热解法将生物质衍生的多孔碳与ZIF-67复合作为优异双功能电催化剂。探究不同热解时间对催化剂性能的影响,发现热解时间为3 h形成Co-N-C催化剂产生了更多缺陷,比表面积高达1210.01 m2·g-1,丰富的微孔和介孔结构为电解质的传输提供更多通道,在ORR性能测试中,其半波电位可达0.81 V,仅次于商用Pt/C催化剂的0.85 V;OER性能在电流密度为10 mA·cm-2时电位是1.73 V,优于商用IrO2催化剂的1.79 V。进一步的理论研究表明富含缺陷Co-N-C催化剂能够有效降低反应势垒,Co与N原子的协同作用促进了ORR反应进行。

, authors=吴凤楠1, 刘冬澳1, 陈禹帆1, 谭思源1, 王寅生2, 杨俊和1, 薛裕华1, 李生娟1, authorsList=吴凤楠, 刘冬澳, 陈禹帆, 谭思源, 王寅生, 杨俊和, 薛裕华, 李生娟, authorCompany=null, correspAuthors=李生娟, authorNote=null, correspAuthorsNote=
李生娟(1975—),女,副教授,博士,研究方向为电催化及电储能,联系地址:上海市杨浦区军工路515号上海理工大学材料与化学学院(200093),E-mail:
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Molecular Catalysis,2023,537:112942., articleTitle=The OER/ORR activities of copper oxyhydroxide series electrocatalysts, refAbstract=null)], funds=[Fund(id=1321967881865248950, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, awardId=51402192, language=CN, fundingSource=国家自然科学基金项目(51402192), fundOrder=null, country=null), Fund(id=1321967881936552119, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, awardId=PKX2023-W01, language=CN, fundingSource=浦东新区科技发展基金项目(PKX2023-W01), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1321967873589887078, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, xref=1., ext=[AuthorCompanyExt(id=1321967873598275687, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, companyId=1321967873589887078, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.School of Materials and Chemistry,University of Shanghai for Science and Technology,Shanghai 200093,China), AuthorCompanyExt(id=1321967873606664296, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, companyId=1321967873589887078, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.上海理工大学 材料与化学学院,上海 200093)]), AuthorCompany(id=1321967873677967465, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, xref=2., ext=[AuthorCompanyExt(id=1321967873682161770, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, companyId=1321967873677967465, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.PhiChem Corporation,Shanghai 201908,China), AuthorCompanyExt(id=1321967873690550379, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, companyId=1321967873677967465, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.上海飞凯材料科技股份有限公司,上海 201908)])], figs=[ArticleFig(id=1321967878270730400, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.1, caption=Synthesis of Co-N-C catalyst material, figureFileSmall=nTMIHevSt4dUs3N2ECf5OA==, figureFileBig=yiLdpNQ1ig4KZsJtlfD22Q==, tableContent=null), ArticleFig(id=1321967878329450657, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图1, caption=Co-N-C催化剂材料合成示意图, figureFileSmall=nTMIHevSt4dUs3N2ECf5OA==, figureFileBig=yiLdpNQ1ig4KZsJtlfD22Q==, tableContent=null), ArticleFig(id=1321967880254636194, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.2, caption=Co-N-C catalysts with pyrolysis time of 1,3,5 h (a)XRD spectra;(b)Raman spectra, figureFileSmall=vev8Oe+5C73oq5Dv7zsh+Q==, figureFileBig=C72WkNiSkDvyVLfT5T8W/Q==, tableContent=null), ArticleFig(id=1321967880325939363, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图2, caption=热解时间为1、3、5 h的Co-N-C催化剂 (a)XRD谱图;(b)Raman谱图, figureFileSmall=vev8Oe+5C73oq5Dv7zsh+Q==, figureFileBig=C72WkNiSkDvyVLfT5T8W/Q==, tableContent=null), ArticleFig(id=1321967880388853924, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.3, caption=Biomass derived carbon precursor and Co-N-C sample with pyrolysis time of 3 h

(a)N2 adsorption-desorption isotherms;(b)pore diameter distribution plots

, figureFileSmall=nhpbK+Fr76kSUId48vDdVw==, figureFileBig=gDlbKyBcSGMD7QhRQwmV7g==, tableContent=null), ArticleFig(id=1321967880489517221, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图3, caption=生物质衍生碳前驱体和热解时间为3 h的Co-N-C样品

(a)N2吸附-脱附等温线;(b)孔径分布图

, figureFileSmall=nhpbK+Fr76kSUId48vDdVw==, figureFileBig=gDlbKyBcSGMD7QhRQwmV7g==, tableContent=null), ArticleFig(id=1321967880606957734, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.4, caption=SEM images of Co-N-C obtained at different pyrolysis time(a)-(c),TEM images(d),(e), figureFileSmall=NeM0nUtwPpcaJW9srJnbdw==, figureFileBig=WFaCOh+zpwhYrbqXtw9M5g==, tableContent=null), ArticleFig(id=1321967880690843815, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图4, caption=不同热解时间获得的Co-N-C的SEM图(a)~(c),热解时间为3 h的Co-N-C的TEM图(d),(e)及元素映射图(f)

and elemental mapping(f) of Co-N-C with pyrolysis time of 3 h

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(a)survey spectrum;(b)C 1s;(c)N 1s;(d)O 1s;(e)Co 2p

, figureFileSmall=XQTo0NO66RMDb1mWRfZN3A==, figureFileBig=Rw+uz8XnrzJ/STowYrnXfw==, tableContent=null), ArticleFig(id=1321967880833450153, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图5, caption=热解时间为3 h的Co-N-C催化剂材料的XPS谱

(a)全谱;(b)C 1s;(c)N 1s;(d)O 1s;(e)Co 2p

, figureFileSmall=XQTo0NO66RMDb1mWRfZN3A==, figureFileBig=Rw+uz8XnrzJ/STowYrnXfw==, tableContent=null), ArticleFig(id=1321967880913141930, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.6, caption=Electrocatalytic property of Co-N-C samples

(a)CV curves with different pyrolysis time;(b)LSV curves with different pyrolysis time;(c)LSV curves with different rotational speeds of Co-N-C samples pyrolyzed for 3 h;(d)K-L diagrams and electron transfer numbers at different potentials of Co-N-C samples pyrolyzed for 3 h

, figureFileSmall=/2Z8rWFWj40Cr28TM3bRDQ==, figureFileBig=KFMAXInIFjsKi0VxCf9qYQ==, tableContent=null), ArticleFig(id=1321967880988639403, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图6, caption=Co-N-C样品的电催化性能

(a)不同热解时间的CV曲线;(b)不同热解时间的LSV曲线;(c)热解3 h的Co-N-C样品在不同转速下的LSV曲线;

(d)热解3 h的Co-N-C样品在不同电位的K-L图及电子转移数

, figureFileSmall=/2Z8rWFWj40Cr28TM3bRDQ==, figureFileBig=KFMAXInIFjsKi0VxCf9qYQ==, tableContent=null), ArticleFig(id=1321967881055748268, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Fig.7, caption=Co-N-C sample with pyrolysis time of 3 h

(a)ring-disk electrode test curve;(b)H2O2 yield and electron transfer number;(c)stability test

, figureFileSmall=hgisWJf9hVos8F2dBpARHQ==, figureFileBig=LRT8p4tX3W6zX80Os+treg==, tableContent=null), ArticleFig(id=1321967881127051437, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=图7, caption=热解时间为3 h的Co-N-C样品

(a)环盘电极测试曲线;(b)H2O2产率和电子转移数;(c)稳定性测试

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(a)Co-C、Co-N-C和Co-N-Cd理论模型;(b)ORR自由能图;(c)Co-N-Cd的差分电荷密度图

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Specific surface area, pore size, and pore volume of biomass-derived carbon precursors and Co-N-C samples pyrolyzed for 3 h

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleSSA/(m2·g-1)

Pore diameter/

nm

Pore volume/

(cm3·g-1)

C1090.192.870.56
Co-N-C1210.012.680.55
), ArticleFig(id=1321967881609396403, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=表1, caption=

生物质衍生碳前驱体和热解3 h的Co-N-C样品的比表面积、孔径和孔容

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleSSA/(m2·g-1)

Pore diameter/

nm

Pore volume/

(cm3·g-1)

C1090.192.870.56
Co-N-C1210.012.680.55
), ArticleFig(id=1321967881680699572, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=EN, label=Table 2, caption=

Comparison of oxygen reduction performance parameters of Co-N-C samples with pyrolysis time of 1,3,5 h

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleOpening electromotive force(vs. RHE)/V

E1/2(vs. RHE)/

V

Limiting current density/(mA·cm-2)
Co-N-C-1 h0.870.764.33
Co-N-C-3 h0.880.815.43
Co-N-C-5 h0.870.784.96
Pt/C0.940.855.42
), ArticleFig(id=1321967881747808437, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321967871572426833, language=CN, label=表2, caption=

热解时间为1、3、5 h的Co-N-C样品的氧还原性能参数对比

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleOpening electromotive force(vs. RHE)/V

E1/2(vs. RHE)/

V

Limiting current density/(mA·cm-2)
Co-N-C-1 h0.870.764.33
Co-N-C-3 h0.880.815.43
Co-N-C-5 h0.870.784.96
Pt/C0.940.855.42
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Co/N共掺杂富含缺陷的生物质衍生多孔碳作为高效OER/ORR双功能电催化剂
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吴凤楠 1 , 刘冬澳 1 , 陈禹帆 1 , 谭思源 1 , 王寅生 2 , 杨俊和 1 , 薛裕华 1 , 李生娟 1
材料工程 | 研究论文 2026,54(6): 200-208
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材料工程 |研究论文 2026 , 54 (6) : 200 -208
Co/N共掺杂富含缺陷的生物质衍生多孔碳作为高效OER/ORR双功能电催化剂
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吴凤楠1, 刘冬澳1, 陈禹帆1, 谭思源1, 王寅生2, 杨俊和1, 薛裕华1, 李生娟1
作者信息
  • 1.上海理工大学 材料与化学学院,上海 200093
  • 2.上海飞凯材料科技股份有限公司,上海 201908
通讯作者:
李生娟(1975—),女,副教授,博士,研究方向为电催化及电储能,联系地址:上海市杨浦区军工路515号上海理工大学材料与化学学院(200093),E-mail:
Co/N co-doped defect-rich biomass-derived porous carbon as an efficient OER/ORR bi-functional electrocatalyst
Fengnan WU1, Dongao LIU1, Yufan CHEN1, Siyuan TAN1, Yinsheng WANG2, Junhe YANG1, Yuhua XUE1, Shengjuan LI1
Affiliations
  • 1.School of Materials and Chemistry,University of Shanghai for Science and Technology,Shanghai 200093,China
  • 2.PhiChem Corporation,Shanghai 201908,China
出版时间: 2026-06-20 doi: 10.11868/j.issn.1001-4381.2024.000176
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开发具有高效析氧反应(OER)和氧还原反应(ORR)的低成本双功能电催化剂在能量转换和存储技术中至关重要。本工作采用球磨法和高温热解法将生物质衍生的多孔碳与ZIF-67复合作为优异双功能电催化剂。探究不同热解时间对催化剂性能的影响,发现热解时间为3 h形成Co-N-C催化剂产生了更多缺陷,比表面积高达1210.01 m2·g-1,丰富的微孔和介孔结构为电解质的传输提供更多通道,在ORR性能测试中,其半波电位可达0.81 V,仅次于商用Pt/C催化剂的0.85 V;OER性能在电流密度为10 mA·cm-2时电位是1.73 V,优于商用IrO2催化剂的1.79 V。进一步的理论研究表明富含缺陷Co-N-C催化剂能够有效降低反应势垒,Co与N原子的协同作用促进了ORR反应进行。

生物质碳材料  /  ZIF-67  /  氧还原反应  /  氧析出反应  /  锌-空气电池

The development of low-cost bi-functional electrocatalysts with efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial in energy conversion and storage technologies. In this study, biomass-derived porous carbon and ZIF-67 are combined as excellent bi-functional electrocatalysts through ball milling and high-temperature pyrolysis. The effect of different pyrolysis time on the catalytic performance is investigated. It is found that the formation of Co-N-C catalyst with pyrolysis time of 3 h produces more defects,and the specific surface area is as high as 1210.01 m2·g-1. The rich microporous and mesoporous structure provides more channels for the transmission of electrolyte. In the ORR performance test,the half-wave potential can reach 0.81 V,second only to 0.85 V of the commercial Pt/C catalyst. The OER performance is 1.73 V at a current density of 10 mA·cm-2,which is better than 1.79 V of the commercial IrO2 catalyst. Further theoretical studies show that the defect-rich Co-N-C catalyst can effectively reduce the reaction barrier,and the synergistic effect of Co and N atoms promotes the ORR reaction.

biomass carbon material  /  ZIF-67  /  oxygen reduction reaction  /  oxygen evolution reaction  /  zinc-air battery
吴凤楠, 刘冬澳, 陈禹帆, 谭思源, 王寅生, 杨俊和, 薛裕华, 李生娟. Co/N共掺杂富含缺陷的生物质衍生多孔碳作为高效OER/ORR双功能电催化剂. 材料工程, 2026 , 54 (6) : 200 -208 . DOI: 10.11868/j.issn.1001-4381.2024.000176
Fengnan WU, Dongao LIU, Yufan CHEN, Siyuan TAN, Yinsheng WANG, Junhe YANG, Yuhua XUE, Shengjuan LI. Co/N co-doped defect-rich biomass-derived porous carbon as an efficient OER/ORR bi-functional electrocatalyst[J]. Journal of Materials Engineering, 2026 , 54 (6) : 200 -208 . DOI: 10.11868/j.issn.1001-4381.2024.000176
不断增长的能源需求和环境持续恶化等问题日益凸显,可再生的清洁能源的开发与利用受到重点关注[1-2]。目前,通过太阳能电池板和风力发电机已经实现了将风能和太阳能转化为电能供人们生产生活使用,这推动着能源存储和转换器件不断革新,如燃料电池、金属-空气电池、超级电容器等新型能源装备[3-4]。其中,金属-空气电池是一种半储能半燃料式电池,特别是锌-空气电池,具备倍率性能好、能量密度大、低碳可持续等优点[5],有望成为电动汽车和便携式电子设备的储能器件[6]。锌-空气电池的阴极上发生的氧还原反应(ORR)和氧析出(OER)是整个电池技术的核心,但该反应动力学过程较为缓慢,高效的催化剂能够有效增强ORR反应动力学。目前,Pt等贵金属是最常用的ORR催化剂[7-8],然而储量低、价格高昂和稳定性差等因素限制了其广泛应用[9]。
近年来,碳材料因其丰富的杂化方式、稳定的物理化学性质、高电导率等优势在电催化领域脱颖而出[10-11]。作为碳材料中的主要组成部分,生物质碳材料不仅成本低廉、可再生和来源广泛,而且含有丰富表面官能团[12],具有构建ORR活性位点所需的大量元素和一些独特的协同环境[13]。一般来说,提高碳材料ORR活性的策略主要包括:(1)设计具有大比表面积和丰富多孔结构的纳米碳材料,通过促进传质来提高催化性能[14-15];(2)在碳材料中引入杂原子来创造更多的活性位点[16];(3)通过提高石墨化程度来改善导电性[17]。沸石咪唑骨架(ZIFs)是由四面体配位的二价金属离子和咪唑盐相互连接组成,在热解过程中,咪唑转化为碳质网络,部分N原子进入碳晶格内形成吡啶-N或吡咯-N[18],使得碳基内部的电子结构发生变化,产生活性化学吸附位点。同时N原子与金属原子配位形成M-N-C活性位点,调节金属原子对O2的吸附/解吸能[19]。Zhao等[20]利用ZnCl2和Zn(OH)2作为致孔剂,在生物质废物碳化过程后成功地获得了一系列具有3D分级多孔结构的N、S双掺杂碳,在碱性介质中测试,半波电位为0.83 V(vs. RHE)并表现出显著的长期稳定性和耐甲醇能力,组装的两个串联的锌空气电池可以在24 h内连续点亮216个LED。Yang等[21]提出了一种简便的低温煅烧改性ZIF-67的ORR活性的途径,控制加热温度可选择性地产生局部缺陷,缺陷的形成激活了ZIF-67的固有Co-N4金属位,提高了ORR电催化性能。
在此基础上,本工作选用云杉树皮作为生物质碳源,经过球磨和热解后形成富含缺陷的多孔碳,并与电化学活性物质ZIF-67形成复合材料,最终热解后形成具有缺陷的Co/N共掺杂C(Co-N-C)催化剂,呈现出疏松多孔碳上负载笼状结构,同时进行了物相分析以及电化学性能测试,Co-N-C催化剂表现出了极其优异的ORR(或OER)活性和长期耐久性。
云杉树皮,产自广东省;六水合硝酸钴(Co(NO3)2·6H2O,AR),2-甲基咪唑(C4H6N2,98%(质量分数,下同)),氯化锌(ZnCl2,AR),氢氧化钾(KOH,AR),无水乙醇(C2H5OH,AR),商用IrO2催化剂(AR),均购自国药集团化学试剂有限公司;Nafion溶液,5%,购自广东烛光新能源有限公司;商用Pt/C催化剂,20%,购自上海河森电气有限公司。
杉树皮粉碎处理:将云杉树皮在70 ℃的烘箱中干燥12 h,干燥后的树皮用球磨机粉碎,设置转速为300 r·min-1,球料比10∶1,球磨时间3 h,得到树皮粉末。
杉树皮高温热解处理:将0.5 g树皮粉末和1.5 g ZnCl2充分混合,在N2气氛下,以5 ℃·min-1速率升温至900 ℃,煅烧3 h后,自然冷却至室温,用去离子水洗涤至中性,70 ℃干燥12 h,得到活化的碳前驱体。
ZIF-67的制备:将2 mmol的Co(NO3)2·6H2O和8 mmol的2-甲基咪唑分别溶解在50 mL的甲醇中,超声分散均匀。然后将2-甲基咪唑甲醇溶液迅速加入Co(NO3)2·6H2O甲醇溶液中,常温磁力搅拌24 h。最后,将离心得到的紫色沉淀分别用甲醇和乙醇多次清洗,在70 ℃烘干12 h,即得到ZIF-67(约60 mg)。
Co-N-C制备:将活化后的C与ZIF-67(C与ZIF-67质量比为3∶1)在研钵中充分研磨混合,然后在管式炉中N2气氛下,以5 ℃·min-1升温至900 ℃,煅烧时间分别设定为1、3、5 h,即得到3种不同热解时间制备的Co-N-C催化剂。
采用SEM(Quanta 450型)和TEM(Tecnai G2 F30型)对样品微观形貌进行表征分析;采用X射线衍射仪(D8 ADVANCE型)对样品物相和结构进行分析;使用激光拉曼光谱仪(Horiba Lab型)采集样品的拉曼光谱;样品的比表面积和孔径结构测试采用氮气吸附/脱附分析仪(Nova2000e型),利用Brunauer-Emmett-Teller(BET)和Barrett-Joyner-Halenda(BJH)模型进行数据处理;利用X射线光电子能谱仪(ESCALAB-250型)对元素成分进行分析;采用电化学工作站(CHI760E型)以及旋转圆盘装置(RDE,PINE AF型)对电化学性能进行测试。
所有样品均采用CHI760E电化学分析仪和Pine旋转圆盘电极进行测量。采用传统的三电极体系,涂覆催化剂的旋转圆盘作为工作电极,饱和甘汞电极和铂片分别作为参比电极和对电极,电解液为0.1 mol·L-1 KOH溶液。将5.0 mg的Co-N-C催化剂分散在由970 μL的无水乙醇和30 μL的Nafion组成的溶液中,超声分散1 h,然后将10 μL催化剂油墨分2次滴加在直径为5 mm玻碳电极上,室温干燥,负载量为0.51 mg·cm-2。为了比较,采用相同程序制备Pt/C与IrO2催化剂用于ORR和OER测试。
在测试前,对0.1 mol·L-1 KOH溶液通入30 min高纯氧气,保证在测试过程中电解液处于氧饱和状态。首先,利用循环伏安法(CV)进行活化,以50 mV·s-1扫描速率测试20圈。在0.2~1.2 V(vs. RHE)电压区间内进行CV测试,扫描速率为10 mV·s-1。然后,在转速为400、625、900、1225、1600、2025 r·min-1进行线性扫描伏安法(LSV)测试,扫描速率为10 mV·s-1。所有电位均根据能斯特方程将饱和甘汞电极(SCE)转换成标准可逆氢电极(RHE)。
所有计算均基于密度泛函理论(density functional theory,DFT)方法,并在维也纳从头算模拟软件包(VASP 5.4.4)中完成,使用PBE泛函的广义梯度近似(generalized gradient approximation,GGA)。平面波能量截断为450 eV,采用2×2×1的Monkhorst-Pack网格对布里渊区进行超级单体结构优化。真空间隙设定为15 Å,以确保足够的真空度,避免两个相邻表面之间的影响,原子松弛的力收敛准则设为0.01 eV·Å-1。材料的ORR催化活性可通过吉布斯自由能(ΔGH)来评价,定义为:ΔG=ΔE+EZP-TΔS,式中:ΔE为总能量,EZP为零点能,T为温度(298.15 K),ΔS是熵的变化,ΔEZP和ΔS由吸附中间体的振动频率计算得到。
图1为Co-N-C催化剂的制备流程示意图,以云山树皮作为生物质碳材料,ZnCl2作为活化剂,通过900 ℃高温热解形成碳前驱体。以溶剂法合成的ZIF-67作为金属源和氮源,将两种材料以一定的比例混合,再次经过高温退火,形成了N掺杂的C包裹Co纳米颗粒的结构。
图2(a)为不同热解时间所制备的Co-N-C电催化剂样品的XRD图谱。在44.2°、51.5°、75.9°处出现的3个较强的衍射峰,分别对应金属Co(JCPDS# 15-0806)的(111)、(200)、(220)晶面,说明热解过程中形成了结晶度较好的Co纳米颗粒[22],C的标准图谱(JCPDS# 41-1487)中在26.6°和44.6°衍射峰对应(002)和(110)晶面,不难发现,样品中C在26.6°的衍射峰向大角度偏移,这意味着晶格常数变小,可能是由于N的原子半径比C小,N掺杂后导致C晶格发生畸变所引起。图2(b)的拉曼光谱图中可以看到2个明显特征峰,D峰(1350 cm-1)代表的是碳原子的晶格缺陷,G峰(1580 cm-1)代表碳原子sp2杂化平面内的伸缩振动,D峰与G峰的强度比值即ID/IG表示催化剂材料缺陷程度[23],通常认为ID/IG值越大,代表材料的缺陷结构越多,热解时间1、3、5 h的Co-N-C样品ID/IG比值分别为1.019、1.023、1.020,表明热解时间为3 h时获得的Co-N-C催化剂的缺陷程度最高,而缺陷处往往存在不饱和键,导致局部电子结构发生改变[24],为ORR反应提供更多活性位点。
利用N2吸脱/脱附曲线分析了生物质衍生碳和热解时间为3 h的Co-N-C样品比表面积大小和结构组成,选取BET模型分析样品的比表面积,选取BJH模型分析材料的孔体积及孔径分布情况。如图3(a)所示,所有样品的氮气吸脱附曲线都具有Ⅳ型特征,在相对压力较低(P/P0<0.1)时,曲线急剧上升,证明存在一定数量的微孔,当相对压力较高(P/P0>0.4)时,可以观察到明显的滞后环,说明Co-N-C催化剂中孔结构主要由微孔和介孔组成[25]。催化剂孔径高度集中在2~4 nm(图3(b))。由表1可以看出,C和Co-N-C的平均孔径分别为2.87 nm和2.68 nm,均为介孔结构。其中Co-N-C的BET比表面积(specific surface area,SSA)达到1210.01 m2·g-1,远高于生物质衍生碳的1090.19 m2·g-1。丰富的介孔结构和高比表面积有助于电催化过程中电解质的迁移,从而加快反应速率。
采用SEM研究Co-N-C催化剂的微观形貌,图4(a)~(c)为不同热解时间制备的Co-N-C催化剂,可以看出仅退火1 h的样品层状C结构边缘有碳纳米管生成的趋势,随着退火时间的延长,C层结构边缘由于Co纳米粒子的催化作用,使得形成一定量的碳纳米管,当退火时间为5 h时,在C结构表面催化生成了大量的碳纳米管,并且发生团聚现象。TEM图清楚显示,热解后形成的Co纳米颗粒被限制在生物质衍生的C壳中(图4(d)),防止了Co纳米颗粒在高温下的团聚,从图4(e)中能明显观察到间距分别为0.20 nm和0.34 nm的晶格条纹,分别属于Co(111)和石墨烯碳(002)晶面,进一步表明Co纳米颗粒的存在。图4(f)显示N原子均匀分布在C层中,而Co纳米颗粒嵌入在N掺杂的C层中。
使用XPS分析了热解3 h的Co-N-C-样品的化学组成和元素含量,图5(a)为XPS总谱,表明样品中存在C、N、O、Co元素,各元素的原子分数分别为90.08%、3.65%、5.44%、0.83%。图5(b)为C 1s谱,在284.4、287.8、289.5 eV结合能处分别对应C—C、C—N、C═O的峰值。在N 1s光谱中(图5(c)),N 1s的结合能可分为4个峰:吡啶氮(398.1 eV),吡咯氮(399.6 eV),石墨氮(401.3 eV),氧化氮(403.1 eV)[26]。吡啶氮和吡咯氮均能提升催化剂的ORR性能,此外石墨氮提高样品的导电性,这也有益于提升催化剂的ORR活性[27]。图5(d)为O 1s谱,在530.5 eV的峰归属于C═O键,在533.1 eV属于C—O键[28],氧元素以含氧官能团的形式存在于材料中,可以提高材料的亲水性,有利于催化剂与电解液充分接触[29]。在图5(e)的Co 2p谱中,在780.2、795.4 eV峰分别对应于Co 2p3/2和Co 2p1/2的结合能[30],证明了单质Co的存在,在787.4、803.5 eV处2个特征峰分别为Co 2p3/2和Co 2p1/2的卫星峰。除此之外,在779.4、795.6 eV峰源于Co3+的存在[31],782.4、797.8 eV峰来源于Co2+的存在,而Co2+与Co3+在ORR反应过程中可以作为氧的吸附和脱附位点。
为了验证样品的ORR活性,在0.1 mol·L-1 KOH溶液中用圆盘电极(RDE)进行电化学性能测试。图6为不同热解时间后Co-N-C催化剂样品的电化学性能测试图。图6(a)为不同热解温度下Co-N-C催化剂样品的CV曲线,可以观察到在0.8 V的电位附近出现明显还原峰,表明具有良好的氧还原性能。图6(b)为Co-N-C样品在1600 r·min-1转速下得到的LSV曲线。当热解时间分别为1、3、5 h时,样品的半波电位(E1/2)分别是0.76、0.81、0.78 V,具体性能参数如表2所示,热解3 h的Co-N-C催化剂显示出较高的半波电位,接近商用Pt/C催化剂(0.85 V),同时,在0.2 V电压下具有更高的氧扩散极限电流密度(5.43 mA·cm-2),这表明热解时间3 h为Co-N-C最佳的工艺条件。在ORR中不同转速下的LSV曲线推导出不同电位下的Koutecky-Levich(K-L)图[32],如图6(c),(d)所示,热解3 h的Co-N-C催化剂K-L曲线表现出良好平行性和线性,表明电子转移数(n)相似,该催化剂上的ORR反应对溶解的O2浓度表现出典型的一级反应动力学[33]。在0.45~0.60 V电压下,电子转移数稳定在3.76~3.90之间,平均值接近于4,表明在ORR反应过程中符合4e-转移过程。
为更好揭示Co-N-C催化剂的ORR反应机理,在0.1 mol·L-1 KOH电解液中以1600 r·min-1转速进行环盘电极(RRDE)测试。如图7(a)所示,Co-N-C的环电流与Pt/C基本一致,而Co-N-C的盘电流的极限电流密度与Pt/C相近。通过盘电流和环电流计算H2O2产率及电子转移数,在0.2~0.7 V电压范围中,Co-N-C的电子转移数为3.80~3.89,略低于Pt/C的3.98~4.00,这与K-L方程计算结果基本保持一致。Co-N-C的H2O2产率在5.52%~10.01%之间,高于Pt/C的0.03%~0.06%,表明Co-N-C催化剂在ORR反应过程中主要为4e-1转移,直接将O2还原为H2O(图7(b))。采用计时电流法(I-t)评估Co-N-C和Pt/C催化剂的定性(图7(c)),在O2中转速1600 r·min-1测定,当反应进行40000 s时,Co-N-C的电流保持了相对于初始值的79.26%,Pt/C仅为初始值的71.41%,这表明Co-N-C在碱性溶液中具有长久的稳定性。
图8(a)显示了Co-N-C、Pt/C及IrO2的线性扫描伏安曲线,在10 mA·cm-2的电流密度下,Co-N-C催化剂表现出最佳的OER性能,对应电位为1.73 V,优于贵金属Pt/C(1.97 V)和IrO2(1.79 V)。图9(b)为OER的塔菲尔(Tafel)曲线,Co-N-C的斜率为226.6 mV·dec-1,介于Pt/C(289.8 mV·dec-1)和IrO2(126.7 mV·dec-1)之间,表明Co-N-C同贵金属相比,具有较快的反应动力学。
通过DFT计算,进一步研究了富含缺陷的Co-N-C的ORR反应机理。如图9(a)所示,以石墨烯结构作为C层[34],分别建立了Co掺杂C(Co-C)、Co/N共掺杂C(Co-N-C)和含C原子缺陷的Co/N共掺杂C(Co-N-Cd)3种不同的催化剂模型。
催化剂ORR活性受*OOH、*O和*OH等中间体的吸附自由能影响[35],以Co为吸附位点的自由能图如图9(b)所示,结果表明,Co-C在O2→*OH过程中表现出4.26 eV的高势垒,N原子的掺杂使得Co-N-C的决速步转变为O的质子化过程(*O→*OH),所需克服势垒仅为0.58 eV,引入C原子缺陷后,Co-N-Cd进一步将决速步吸附能减小为0.47 V,这表明富含缺陷的Co-N-Cd催化剂能够有效降低ORR反应阻力。从图9(c)的Co-N-Cd差分电荷密度图可以看到,在N原子周围的电荷耗尽(蓝色区域),而在Co原子周围电荷积累(黄色区域),这一电子转移过程是提升催化剂ORR活性的关键因素。
(1)利用生物质碳和ZIF-67热解制备了一种经济环保、价格低廉和性能优异的ORR催化剂。生物质碳化后形成的多孔碳结构促进电解质中离子的传输,ZIF-67演变成的Co纳米颗粒成为主要的催化活性位点。
(2)在碳化温度为900 ℃下,探究出热解时间为3 h制备的Co-N-C催化剂表现出最佳的ORR和OER双功能催化活性。Co-N-C的ORR半波电位达0.81 V,仅次于贵金属催化剂Pt/C,持续运行40000 s后,电流保持率为79.26%;OER的反应动力学远高于Pt/C。
(3)DFT计算表明,缺陷的存在可以有效降低ORR反应势垒,提高催化剂的活性。
  • 国家自然科学基金项目(51402192)
  • 浦东新区科技发展基金项目(PKX2023-W01)
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doi: 10.11868/j.issn.1001-4381.2024.000176
  • 接收时间:2024-03-12
  • 首发时间:2026-10-27
  • 出版时间:2026-06-20
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  • 收稿日期:2024-03-12
  • 录用日期:2024-04-28
基金
国家自然科学基金项目(51402192)
浦东新区科技发展基金项目(PKX2023-W01)
作者信息
    1.上海理工大学 材料与化学学院,上海 200093
    2.上海飞凯材料科技股份有限公司,上海 201908

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李生娟(1975—),女,副教授,博士,研究方向为电催化及电储能,联系地址:上海市杨浦区军工路515号上海理工大学材料与化学学院(200093),E-mail:
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2种不同金属材料的力学参数
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属
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占总种数比例
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species (%)
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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