【《过渡金属硫族化合物研究的文献综述》4400字】

过渡金属硫族化合物研究的文献综述目录TOC\o"1-3"\h\u25947过渡金属硫族化合物研究的文献综述 172701.1概述 133471.2相转化 1167201.3点缺陷 2314171.4HER催化反应的研究进展 3208171.5晶格掺杂剂 41.1概述从实现石墨烯分离之后，随着半导体和绝缘体的实现，2D材料的应用范围已急剧扩大。层状过渡金属硫族化合物（TMDs）以石墨状的层状结构结晶ADDINEN.CITEADDINEN.CITE.DATA[21-24]，导致其电学、化学、机械和热学性能具有强烈的各向异性ADDINEN.CITE<EndNote><Cite><Author>Wilson</Author><Year>1975</Year><RecNum>1738</RecNum><DisplayText><styleface="superscript">[25]</style></DisplayText><record><rec-number>1738</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615173574">1738</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wilson,J.A.</author><author>DiSalvo,F.J.</author><author>Mahajan,S.</author></authors></contributors><titles><title>Charge-densitywavesandsuperlatticesinthemetalliclayeredtransitionmetaldichalcogenides</title><secondary-title>AdvancesinPhysics</secondary-title></titles><periodical><full-title>AdvancesinPhysics</full-title></periodical><pages>117-201</pages><volume>24</volume><number>2</number><section>117</section><dates><year>1975</year></dates><isbn>0001-8732 1460-6976</isbn><urls></urls><electronic-resource-num>10.1080/00018737500101391</electronic-resource-num></record></Cite></EndNote>[25]，应用在很多方向，如氢析出反应，CO2还原反应ADDINEN.CITE<EndNote><Cite><Author>Kang</Author><Year>2020</Year><RecNum>149</RecNum><DisplayText><styleface="superscript">[26]</style></DisplayText><record><rec-number>149</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1609596387">149</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kang,Sungwoo</author><author>Ju,Suyeon</author><author>Han,Seungwu</author><author>Kang,Youngho</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">ComputationalIdentificationofTransition-MetalDichalcogenidesforElectrochemicalCO</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">ReductiontoHighlyReducedSpeciesBeyondCOandHCOOH</style></title><secondary-title>TheJournalofPhysicalChemistryC</secondary-title></titles><periodical><full-title>TheJournalofPhysicalChemistryC</full-title></periodical><pages>25812-25820</pages><volume>124</volume><number>47</number><section>25812</section><dates><year>2020</year></dates><isbn>1932-7447 1932-7455</isbn><urls></urls><electronic-resource-num>10.1021/acs.jpcc.0c07113</electronic-resource-num></record></Cite></EndNote>[26],氧还原反应ADDINEN.CITEADDINEN.CITE.DATA[27]和氮还原反应ADDINEN.CITEADDINEN.CITE.DATA[28]。TMDs是可以分离成层的半导体，其结构组成一般可以用AB2表示（A：过渡金属，B：S族非金属）。普通的TMD是两层B位原子夹一层A位原子结构。研究表明，单个层可以通过像石墨烯那样的纹波结构来稳定ADDINEN.CITE<EndNote><Cite><Author>Bertolazzi</Author><Year>2011</Year><RecNum>1740</RecNum><DisplayText><styleface="superscript">[29,30]</style></DisplayText><record><rec-number>1740</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615174007">1740</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bertolazzi,Simone</author><author>Brivio,Jacopo</author><author>Kis,Andras</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">StretchingandbreakingofultrathinMoS</style><styleface="subscript"font="default"size="100%">2</style></title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>9703-9709</pages><volume>5</volume><number>12</number><dates><year>2011</year></dates><urls></urls></record></Cite><Cite><Author>Meyer</Author><Year>2007</Year><RecNum>1739</RecNum><record><rec-number>1739</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615173993">1739</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Meyer,JannikC</author><author>Geim,A.K.</author><author>Katsnelson,MI</author><author>Novoselov,KS</author><author>Booth,TJ</author><author>Roth,S.T%JNature</author></authors></contributors><titles><title>Thestructureofsuspendedgraphemesheets</title><secondary-title>Nature</secondary-title></titles><periodical><full-title>Nature</full-title></periodical><pages>60-3</pages><volume>446</volume><number>7131</number><dates><year>2007</year></dates><urls></urls></record></Cite></EndNote>[29,30]。金属和非金属的化合价分别为+4和-2。A-A键长约为3.15Å到4.03Å，金属和硫族非金属的体积不同，则键长不同ADDINEN.CITE<EndNote><Cite><Author>Chhowalla</Author><Year>2013</Year><RecNum>1742</RecNum><DisplayText><styleface="superscript">[31]</style></DisplayText><record><rec-number>1742</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615174474">1742</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chhowalla,Manish</author><author>Shin,HyeonSuk</author><author>Eda,Goki</author><author>Li,LainJong</author><author>Loh,KianPing</author><author>Zhang,Hua%JNatureChemistry</author></authors></contributors><titles><title>Thechemistryoftwo-dimensionallayeredtransitionmetaldichalcogenidenanosheets</title><secondary-title>NatureChemistry</secondary-title></titles><periodical><full-title>NatureChemistry</full-title><abbr-1>NatChem</abbr-1></periodical><pages>263-275</pages><volume>5</volume><number>4</number><dates><year>2013</year></dates><urls></urls></record></Cite></EndNote>[31]。在TMDs中，超薄的薄片结构暴露了棱柱边缘和基面，而由金属或硫原子终止的边缘取决于生长环境的化学势所定义的形态。因此，通过精确地控制生长条件，可以调整边缘结构，进而可以改变表面的化学性质ADDINEN.CITE<EndNote><Cite><Author>Zhu</Author><Year>2018</Year><RecNum>143</RecNum><DisplayText><styleface="superscript">[24]</style></DisplayText><record><rec-number>143</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1609592773">143</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhu,C.R.</author><author>Gao,D.</author><author>Ding,J.</author><author>Chao,D.</author><author>Wang,J.</author></authors></contributors><auth-address>DepartmentofMaterialScienceandEngineering,NationalUniversityofSingapore,EngineeringDrive3,117575,Singapore.msewangj@.sg.</auth-address><titles><title>TMD-basedhighlyefficientelectrocatalystsdevelopedbycombinedcomputationalandexperimentalapproaches</title><secondary-title>ChemSocRev</secondary-title></titles><periodical><full-title>ChemSocRev</full-title></periodical><pages>4332-4356</pages><volume>47</volume><number>12</number><edition>2018/05/05</edition><dates><year>2018</year><pub-dates><date>Jun18</date></pub-dates></dates><isbn>1460-4744(Electronic) 0306-0012(Linking)</isbn><accession-num>29725691</accession-num><urls><related-urls><url>/pubmed/29725691</url></related-urls></urls><electronic-resource-num>10.1039/c7cs00705a</electronic-resource-num></record></Cite></EndNote>[24]。此外，当三层B-A-B薄片横向尺寸减小时，会产生具有低配位阶梯边缘和角原子的纳米片，从而引起额外的局部化学效应。一旦纳米片上的原子密度下降到临界尺寸以下，边缘原子和角原子就可以在很大程度上控制基面原子，因此可以通过修改边缘原子来控制纳米团簇的平衡形状。AB2纳米片边缘的“缺失”协调（有时也被称为“开放位点”）产生了金属边缘态，这对催化有着重要的意义。量子尺寸效应同样会诱导价带和氧化电位的转移，从而使得体带结构中没有催化活性。1.2相转化TMDs通常有三种已知的相，即1T、2H和3R，其中1T定义为过渡金属原子配位为八面体的相，而2H和3R相为三棱柱状，数字表示层数，而字母T、H和R代表四边形、六边形和菱形晶格。一个单一的TMD具有多态性，这取决于它的形成历史。例如，天然二硫化钼通常存在于2H相中，而合成的MoS2通常含有3R相ADDINEN.CITE<EndNote><Cite><Author>Wilson</Author><Year>1969</Year><RecNum>1743</RecNum><DisplayText><styleface="superscript">[32]</style></DisplayText><record><rec-number>1743</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615174749">1743</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wilson,J.A.</author><author>Yoffe,A.D.%JAdvancesinPhysics</author></authors></contributors><titles><title>Thetransitionmetaldichalcogenidesdiscussionandinterpretationoftheobservedoptical,electricalandstructuralproperties</title><secondary-title>AdvancesinPhysics</secondary-title></titles><periodical><full-title>AdvancesinPhysics</full-title></periodical><pages>193-335</pages><volume>18</volume><number>73</number><dates><year>1969</year></dates><urls></urls></record></Cite></EndNote>[32]。对于单层而言，由于过渡金属原子与其相邻S族原子之间配位方式的不同，存在1H和1T两种相态，其他更奇特的结构形式也可以构建，但由于其较高的能量和不稳定性，很少发现其存在。1H相是最常被发现的，也是室温下热力学上最稳定的构型。它的金属原子在中间，上、下两层为S族非金属，采用三棱柱形，1T相具有较高的能量，为八面体配位。这种多形体的构型也可以理解为在1H相中有一层S原子的横向位移，使S位置相对于金属原子的位置发生偏移。在实验工作中，已经实现通过使用Li夹层材料来稳定1T形式ADDINEN.CITE<EndNote><Cite><Author>Py</Author><Year>1983</Year><RecNum>1749</RecNum><DisplayText><styleface="superscript">[33]</style></DisplayText><record><rec-number>1749</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615193553">1749</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Py,M.A.</author><author>Haering,R.R.</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">StructuraldestabilizationinducedbylithiumintercalationinMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">andrelatedcompounds</style></title><secondary-title>CanadianJournalofPhysics</secondary-title></titles><periodical><full-title>CanadianJournalofPhysics</full-title></periodical><pages>76-84</pages><volume>61</volume><number>1</number><dates><year>1983</year></dates><urls></urls></record></Cite></EndNote>[33]。1.3点缺陷在晶格表面可能会发生单个或者团簇的结构缺陷，被称为点缺陷。在二维TMDs中，不包含外来原子的点缺陷主要有两种类型：第一种是空穴，金属（M）、硫族非金属（X）或MXn团簇从原始晶格中移除；另外就是反位缺陷，非金属取代了金属的位置。TMDs中最常见的空穴形式是失去一个硫族化合物原子。在MoS2中，S原子损耗是普遍的，可以发生在顶层和底层。通过降低对比度，这种S原子的丢失可以在AC-TEM图像中检测到，在ADF-STEM图像中检测得更清楚，如图1-3aADDINEN.CITEADDINEN.CITE.DATA[34-36]。在1S空位附近很少发生应变或键重建。同一列中同时丢失上下两个非金属原子也会发生，但是这种情况出现的更少，如图1-3b，这将导致空穴周围键的收缩，形成局部结构的畸变。在TMDs的TEM成像过程中，很快的发生S原子损失，撞击阈值约为6.5eV，80kV电压的情况下加速电子可以实现这一现象ADDINEN.CITE<EndNote><Cite><Author>Zan</Author><Year>2013</Year><RecNum>1756</RecNum><DisplayText><styleface="superscript">[37]</style></DisplayText><record><rec-number>1756</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615195812">1756</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zan,Recep</author><author>Ramasse,QuentinM</author><author>Jalil,Rashid</author><author>Georgiou,Thanasis</author><author>Novoselov,Kostya</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">ControlofRadiationDamageinMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">byGrapheneEncapsulation</style></title><secondary-title>ACSNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>10167-74</pages><volume>7</volume><number>11</number><dates><year>2013</year></dates><urls></urls></record></Cite></EndNote>[37]，然而，S原子损耗可以在较低的加速电压（即60千伏）下通过更复杂的机制发生，如化学蚀刻效应和可能的电离诱导退化。Mo空穴在能量上是不稳定的，因为一旦一个Mo原子丢失，它的邻近的S原子很容易同时丢失，取而代之形成VMoS3和VMoS6，如图1-3c。图1-3d表示空穴的结构模型。近年来的研究表明，双层MoS2的顶部和底部都有S空位，这表明电子束辐射造成原子损失的机理相当复杂ADDINEN.CITE<EndNote><Cite><Author>Zhou</Author><Year>2017</Year><RecNum>1757</RecNum><DisplayText><styleface="superscript">[38]</style></DisplayText><record><rec-number>1757</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615207665">1757</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhou,Si</author><author>Wang,Shanshan</author><author>Li,Huashan</author><author>Xu,Wenshuo</author><author>Gong,Chuncheng</author><author>Grossman,JeffreyC.</author><author>Warner,JamieH.%JAcsOmega</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">AtomicStructureandDynamicsofDefectsin2DMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">Bilayers</style></title><secondary-title>PhysicalReviewB</secondary-title></titles><periodical><full-title>PhysicalReviewB</full-title><abbr-1>PhysRevB</abbr-1></periodical><pages>3315-3324</pages><volume>2</volume><number>7</number><dates><year>2017</year></dates><urls></urls></record></Cite></EndNote>[38]。通常撞击损伤是以背面的原子为主ADDINEN.CITE<EndNote><Cite><Author>Komsa</Author><Year>2013</Year><RecNum>1758</RecNum><DisplayText><styleface="superscript">[36]</style></DisplayText><record><rec-number>1758</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615207826">1758</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Komsa,HannuPekka</author><author>Kurasch,Simon</author><author>Lehtinen,Ossi</author><author>Kaiser,Ute</author><author>Krasheninnikov,ArkadyV.%JPhysicalReviewB</author></authors></contributors><titles><title>:Evolutionofatomicstructureunderelectronirradiation</title><secondary-title>PhysicalReviewB</secondary-title></titles><periodical><full-title>PhysicalReviewB</full-title><abbr-1>PhysRevB</abbr-1></periodical><pages>035301</pages><volume>88</volume><number>3</number><dates><year>2013</year></dates><urls></urls></record></Cite></EndNote>[36]（大部分的原子损失都会发生在此处），但在顶层观察到的S原子损失表明，要么空位可以在TMD层之间迁移，要么S原子损失是发生在顶层和底层，这表明它不是简单的敲击溅射。空缺对材料的电子、光学和磁性有很大的影响。它们可以作为电子的强散射中心，降低MoS2总体载流子的迁移率。多层MoS2中的S空位作为给电子体，在能带隙中诱导局域态。此外，之前的工作表明，CVD合成的WS2中W和S空位的不均匀分布导致了单晶薄片上PL发射的分割，这是由于W空穴产生的深陷阱态和S空穴产生的浅捐助态ADDINEN.CITE<EndNote><Cite><Author>Hong</Author><Year>2015</Year><RecNum>1760</RecNum><DisplayText><styleface="superscript">[39,40]</style></DisplayText><record><rec-number>1760</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615208477">1760</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hong,Jinhua</author><author>Hu,Zhixin</author><author>Probert,Matt</author><author>Li,Kun</author><author>Lv,Danhui</author><author>Yang,Xinan</author><author>Gu,Lin</author><author>Mao,Nannan</author><author>Feng,Qingliang</author><author>Xie,Liming%JNatureCommunications</author></authors></contributors><titles><title>Exploringatomicdefectsinmolybdenumdisulphidemonolayers</title><secondary-title>NatureCommunications</secondary-title></titles><periodical><full-title>NatureCommunications</full-title><abbr-1>NatCommun</abbr-1></periodical><pages>6293</pages><volume>6</volume><dates><year>2015</year></dates><urls></urls></record></Cite><Cite><Author>Hye</Author><Year>2017</Year><RecNum>1759</RecNum><record><rec-number>1759</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615208464">1759</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hye</author><author>Yun</author><author>Jeong</author><author>Youngjo</author><author>Jin</author><author>Seok</author><author>Joon</author><author>Yun</author><author>Jiong</author><author>Zhao%JAdvancedMaterials</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">HeterogeneousDefectDomainsinSingle-CrystallineHexagonalWS</style><styleface="subscript"font="default"size="100%">2</style></title><secondary-title>AdvancedMaterials</secondary-title></titles><periodical><full-title>AdvancedMaterials</full-title><abbr-1>AdvMater</abbr-1></periodical><pages>1605043</pages><dates><year>2017</year></dates><urls></urls></record></Cite></EndNote>[39,40]。图1-3单层MoS2空穴的ADF-STEM图像及原子模型ADDINEN.CITE<EndNote><Cite><Author>Shanshan</Author><Year>2018</Year><RecNum>1751</RecNum><DisplayText><styleface="superscript">[34]</style></DisplayText><record><rec-number>1751</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615195059">1751</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Shanshan</author><author>Wang</author><author>Alex</author><author>Robertson</author><author>Jamie</author><author>H.</author><author>Warner%JChemicalSocietyReviews</author></authors></contributors><titles><title>Atomicstructureofdefectsanddopantsin2Dlayeredtransitionmetaldichalcogenides</title><secondary-title>ChemicalSocietyReviews</secondary-title></titles><periodical><full-title>ChemicalSocietyReviews</full-title></periodical><pages>6764-6794</pages><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[34]Fig.1-3ADF-STEMimagesandatomicmodelsofmonolayerMoS2cavitiesADDINEN.CITE<EndNote><Cite><Author>Shanshan</Author><Year>2018</Year><RecNum>1751</RecNum><DisplayText><styleface="superscript">[34]</style></DisplayText><record><rec-number>1751</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615195059">1751</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Shanshan</author><author>Wang</author><author>Alex</author><author>Robertson</author><author>Jamie</author><author>H.</author><author>Warner%JChemicalSocietyReviews</author></authors></contributors><titles><title>Atomicstructureofdefectsanddopantsin2Dlayeredtransitionmetaldichalcogenides</title><secondary-title>ChemicalSocietyReviews</secondary-title></titles><periodical><full-title>ChemicalSocietyReviews</full-title></periodical><pages>6764-6794</pages><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[34]1.4HER催化反应的研究进展 TMD材料被认为是一种相对有前景的催化剂构成材料。然而，由于边缘结构少，它们原本的结构形式在HER中的催化效率并不高，纳米结构TMDs已被用于提高边缘结构的浓度进而增加催化活性。理论计算也表明，MoS2纳米片的边缘是活跃的ADDINEN.CITEADDINEN.CITE.DATA[41-43]。人们使用"火山图"来总结相关催化剂的活性。为了找到合适的替代Pt基催化剂（廉价，电化学稳定和环境友好），Norskøv和合作者ADDINEN.CITE<EndNote><Cite><Author>Norskov</Author><Year>2005</Year><RecNum>1717</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>1717</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1614823250">1717</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Norskov,J.K.</author><author>Bligaard,T.</author><author>Logadottir,A.</author><author>Kitchin,J.R.</author><author>Chen,J.G.</author><author>Pandelov,S.</author><author>Stimming,U.</author></authors></contributors><titles><title>TrendsintheExchangeCurrentforHydrogenEvolution</title><secondary-title>Cheminform</secondary-title></titles><periodical><full-title>Cheminform</full-title></periodical><pages>J23-J26</pages><volume>152</volume><number>3</number><dates><year>2005</year></dates><isbn>0013-4651</isbn><urls><related-urls><url>/10.1149/1.1856988</url></related-urls></urls><electronic-resource-num>10.1149/1.1856988</electronic-resource-num></record></Cite></EndNote>[6]使用DFT建立一个HER活性的预测模型，在此基础上计算吸附能量。根据他们的计算，对片状MoS2的边缘位点预测了相当高的活性。结果表明，MoS2的氢结合能位于接近火山曲线的顶部，随后也通过了电化学测量的验证了三棱柱形（2H）MoS2晶体的金属边缘具有电催化活性，而基面则保持惰性ADDINEN.CITEADDINEN.CITE.DATA[44]。 除了制作纳米材料外，通过对MoS2基面进行修饰，也可以明显增加其HER活性。例如，缺陷工程是一种有效的方法在表面产生结构畸形ADDINEN.CITEADDINEN.CITE.DATA[45-47]，可以通过产生额外的不饱和S原子来增加催化活性。有些人通过将半导体性质的2H态MoS2转化为金属性质的1T相态ADDINEN.CITEADDINEN.CITE.DATA[48-51]。例如，QTang等人ADDINEN.CITE<EndNote><Cite><Author>Tang</Author><Year>2016</Year><RecNum>1763</RecNum><DisplayText><styleface="superscript">[3]</style></DisplayText><record><rec-number>1763</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615344462">1763</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>QTang</author><author>DEJiang</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">MechanismofHydrogenEvolutionReactionon1T-MoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">fromFirstPrinciples</style></title><secondary-title>AcsCatalysis</secondary-title></titles><periodical><full-title>ACSCatalysis</full-title></periodical><pages>4953-4961</pages><volume>6</volume><number>8</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[3]使用密度泛函理论计算的方法证明1T相态下基面具有更高的催化活性，研究了1T相态中HER反应的机制，发现表面的氢覆盖度在12.5%到25%之间时，H更倾向于与硫原子结合，这时，氢析出反应更容易发生。通过热力学和动力学能垒以及Tafel斜率的计算，发现HER的主要过程是Volmer−Heyrovsky，即氢吸附在表面之后，更倾向于得到电子，与周围的氢离子结合形成氢气分子。另外，使用其他元素掺杂的方法，同样可以增加基面的催化活性ADDINEN.CITEADDINEN.CITE.DATA[52-54]，主要有三种方式。第一种是过渡金属掺杂，BYoosuk等人ADDINEN.CITE<EndNote><Cite><Author>Yoosuk</Author><Year>2008</Year><RecNum>1764</RecNum><DisplayText><styleface="superscript">[55]</style></DisplayText><record><rec-number>1764</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615346985">1764</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yoosuk,Boonyawan</author><author>Kim,JaeHyung</author><author>Song,Chunshan</author><author>Ngamcharussrivichai,Chawalit</author><author>Prasassarakich,Pattarapan%JCatalysisToday</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">HighlyactiveMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">,CoMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">andNiMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">unsupportedcatalystspreparedbyhydrothermalsynthesisforhydrodesulfurizationof4,6-dimethyldibenzothiophene</style></title><secondary-title>CatalysisToday</secondary-title></titles><pages>14-23</pages><volume>130</volume><number>1</number><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[55]使用水热合成的方法合成MoS2，M/MoS2（M=Co,Ni），测得Me/MoS2具有更好的HER活性。Merki,Daniel等人ADDINEN.CITE<EndNote><Cite><Author>Merki</Author><Year>2012</Year><RecNum>1765</RecNum><DisplayText><styleface="superscript">[56]</style></DisplayText><record><rec-number>1765</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1615347040">1765</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Merki</author><author>D.</author><author>Vrubel</author><author>H.</author><author>Rovelli</author><author>L.</author><author>Fierro</author><author>S.</author><author>X.%JCHEMICALSCIENCE</author></authors></contributors><titles><title>Fe,Co,andNiionspromotethecatalyticactivityofamorphousmolybdenumsulfidefilmsforhydrogenevolution</title><secondary-title>ChemicalScience</secondary-title></titles><periodical><full-title>ChemicalScience</full-title><abbr-1>ChemSci</abbr-1></periodical><pages>2515-2525</pages><dates><year>2012</year></dates><urls></urls></record></Cite></EndNote>[56]使用电化学方法制备出非晶态三硫化钼薄膜M–MoS3（M=Mn,Fe,Co,Ni,Cu,Zn），证明部分掺杂剂（铁，钴和镍）对材料催化活性的提高有明显效果。第二种是非金属掺杂，HuangXADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2017</Year><RecNum>131</RecNum><DisplayText><styleface="superscript">[57]</style></DisplayText><record><rec-number>131</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1607823330">131</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Xiaolei</author><author>Leng,Mei</author><author>Xiao,Wen</author><author>Li,Meng</author><author>Ding,Jun</author><author>Tan,TeckLeong</author><author>Lee,WeeSiangVincent</author><author>Xue,Junmin</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">ActivatingBasalPlanesandS-TerminatedEdgesofMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">towardMoreEfficientHydrogenEvolution</style></title><secondary-title>AdvancedFunctionalMaterials</secondary-title></titles><periodical><full-title>AdvancedFunctionalMaterials</full-title></periodical><pages>1604943</pages><volume>27</volume><number>6</number><section>1604943</section><dates><year>2017</year></dates><isbn>1616301X</isbn><urls></urls><electronic-resource-num>10.1002/adfm.201604943</electronic-resource-num></record></Cite></EndNote>[57]通过研究发现，P掺杂在MoS2基面可以有效降低临近Mo原子的价电子，进而激活周围的基面硫位点和边缘硫位点。JunfengXieADDINEN.CITE<EndNote><Cite><Author>Xie</Author><Year>2013</Year><RecNum>136</RecNum><DisplayText><styleface="superscript">[58]</style></DisplayText><record><rec-number>136</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1607823354">136</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xie,J.</author><author>Zhang,J.</author><author>Li,S.</author><author>Grote,F.</author><author>Zhang,X.</author><author>Zhang,H.</author><author>Wang,R.</author><author>Lei,Y.</author><author>Pan,B.</author><author>Xie,Y.</author></authors></contributors><auth-address>HefeiNationalLaboratoryforPhysicalSciencesattheMicroscale,DepartmentofChemistry,UniversityofScienceandTechnologyofChina,Hefei,Anhui230026,People'sRepublicofChina.</auth-address><titles><title><styleface="normal"font="default"size="100%">Controllabledisorderengineeringinoxygen-incorporatedMoS</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">ultrathinnanosheetsforefficienthydrogenevolution</style></title><secondary-title>JAmChemSoc</secondary-title></titles><periodical><full-title>JAmChemSoc</full-title></periodical><pages>17881-8</pages><volume>135</volume><number>47</number><edition>2013/11/07</edition><dates><year>2013</year><pub-dates><date>Nov27</date></pub-dates></dates><isbn>1520-5126(Electronic) 0002-7863(Linking)</isbn><accession-num>24191645</accession-num><urls><related-urls><url>/pubmed/24191645</url></related-urls></urls><electronic-resource-num>10.1021/ja408329q</electronic-resource-num></record></Cite></EndNote>[58]采用可控无序工程和氧掺杂的方法，研制了一种具有一定无序度的优化催化剂。LiuPADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2017</Year><RecNum>137</RecNum><DisplayText><styleface="superscript">[59]</style></DisplayText><record><rec-number>137</rec-number><foreign-keys><keyapp="EN"db-id="txsz9p99e9pxaves52ex9px6aea2asreawza"timestamp="1607823362">137</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors