【《碳化钼析氢催化剂的研究与发展综述》9100字】

碳化钼析氢催化剂的研究与发展综述目录TOC\o"1-3"\h\u15958碳化钼析氢催化剂的研究与发展综述 1166171.1.1碳化钼的结构与形成 1161901.1.2碳化钼的制备方法 43901.1.3提升碳化钼析氢性能的策略 7过渡金属碳化物是由碳原子插入过渡金属晶格中，形成面心立方（fcc）或六方密堆积（hcp）、简单六方（hex）结构的一类间隙性化合物，其晶体结构如图1.4。碳插入到金属-金属晶格中，拉长了金属-金属的距离，导致金属原子的d带结构发生变化，体现出与Pt相似的电子结构，因而过渡金属碳化物被称为“类铂催化剂”，在材料科学领域得到了广泛的应用。图1.4几种过渡金属碳化物的典型晶体结构[ADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2017</Year><RecNum>198</RecNum><DisplayText><styleface="superscript">41</style></DisplayText><record><rec-number>198</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854771">198</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Yufei</author><author>Guan,Guoqing</author><author>Hao,Xiaogang</author><author>Cao,Ji</author><author>Abudula,Abuliti</author></authors></contributors><titles><title>Molybdenumcarbideasalternativecatalystforhydrogenproduction–Areview</title><secondary-title>RenewableandSustainableEnergyReviews</secondary-title></titles><periodical><full-title>RenewableandSustainableEnergyReviews</full-title></periodical><pages>1101-1129</pages><volume>75</volume><section>1101</section><dates><year>2017</year></dates><isbn>13640321</isbn><urls></urls><electronic-resource-num>10.1016/j.rser.2016.11.092</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">42</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Mo2C</style><styleface="normal"font="default"charset="134"size="100%">综述</style></research-notes></record></Cite></EndNote>41]Figure1.4Typicalcrystalstructureofsometransitionmetalcarbides[ADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2017</Year><RecNum>198</RecNum><DisplayText><styleface="superscript">41</style></DisplayText><record><rec-number>198</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854771">198</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Yufei</author><author>Guan,Guoqing</author><author>Hao,Xiaogang</author><author>Cao,Ji</author><author>Abudula,Abuliti</author></authors></contributors><titles><title>Molybdenumcarbideasalternativecatalystforhydrogenproduction–Areview</title><secondary-title>RenewableandSustainableEnergyReviews</secondary-title></titles><periodical><full-title>RenewableandSustainableEnergyReviews</full-title></periodical><pages>1101-1129</pages><volume>75</volume><section>1101</section><dates><year>2017</year></dates><isbn>13640321</isbn><urls></urls><electronic-resource-num>10.1016/j.rser.2016.11.092</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">42</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Mo2C</style><styleface="normal"font="default"charset="134"size="100%">综述</style></research-notes></record></Cite></EndNote>41].碳化钼的结构与形成碳化钼属于典型的过渡金属碳化物，其钼原子与碳原子的键合囊括了三种形式：金属钼之间形成的金属键、金属钼与非金属碳之间的共价键以及以钼碳电荷转移形成的离子键[ADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2017</Year><RecNum>198</RecNum><DisplayText><styleface="superscript">41</style></DisplayText><record><rec-number>198</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854771">198</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Yufei</author><author>Guan,Guoqing</author><author>Hao,Xiaogang</author><author>Cao,Ji</author><author>Abudula,Abuliti</author></authors></contributors><titles><title>Molybdenumcarbideasalternativecatalystforhydrogenproduction–Areview</title><secondary-title>RenewableandSustainableEnergyReviews</secondary-title></titles><periodical><full-title>RenewableandSustainableEnergyReviews</full-title></periodical><pages>1101-1129</pages><volume>75</volume><section>1101</section><dates><year>2017</year></dates><isbn>13640321</isbn><urls></urls><electronic-resource-num>10.1016/j.rser.2016.11.092</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">42</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Mo2C</style><styleface="normal"font="default"charset="134"size="100%">综述</style></research-notes></record></Cite></EndNote>41]。因此，碳化钼良好地结合了过渡金属、共价化合物和离子晶体三种不同类别材料的特性，不仅具有类似于过渡金属的电子特性和导电性，还有与共价化合物相似的高硬度和耐磨性、与离子晶体相似的高熔点，因而被广泛应用于加氢及制氢反应、氧还原反应、异构化反应等多个催化领域。2012年，Vrubel和Hu等[ADDINEN.CITE<EndNote><Cite><Author>Vrubel</Author><Year>2012</Year><RecNum>12</RecNum><DisplayText><styleface="superscript">42</style></DisplayText><record><rec-number>12</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1587716079">12</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Vrubel,H.</author><author>Hu,X.</author></authors></contributors><auth-address>LaboratoryofInorganicSynthesisandCatalysis,InstituteofChemicalSciencesandEngineering,EcolePolytechniqueFederaledeLausanne,ISIC-LSCI,BCH3305,Lausanne1015,Switzerland.</auth-address><titles><title>Molybdenumborideandcarbidecatalyzehydrogenevolutioninbothacidicandbasicsolutions</title><secondary-title>AngewChemIntEdEngl</secondary-title></titles><periodical><full-title>AngewChemIntEdEngl</full-title></periodical><pages>12703-6</pages><volume>51</volume><number>51</number><edition>2012/11/13</edition><dates><year>2012</year><pub-dates><date>Dec14</date></pub-dates></dates><isbn>1521-3773(Electronic) 1433-7851(Linking)</isbn><accession-num>23143996</accession-num><urls><related-urls><url>/pubmed/23143996</url></related-urls></urls><electronic-resource-num>10.1002/anie.201207111</electronic-resource-num><research-notes>43-firstHERofMo2C</research-notes></record></Cite></EndNote>42]证实了商业微米Mo2C颗粒在酸、碱性电解质溶液中较高的催化活性和稳定性，此外，碳化钼良好的耐酸碱腐蚀性，对于发展全pH范围内的电解水析氢催化剂来说意义重大。从化学组成上来看，根据碳钼原子比的差异，碳化钼具有MoC、Mo2C和MoxCy之分[ADDINEN.CITEADDINEN.CITE.DATA43,44]。当间隙碳原子占据所有的钼原子八面体空隙时形成MoC，而Mo2C是由碳原子占据一半的空隙形成，MoxCy出现的情况较少，碳与钼以非化学计量比的形式存在，彰显了碳化钼组成可灵活调节的优势。晶型上，碳化钼常以β-Mo2C、γ-MoC、η-MoC、α-MoC1-x的形式出现，通过调整碳钼比、碳化条件，就可以得到不同晶型的碳化钼[ADDINEN.CITEADDINEN.CITE.DATA43,45]。Wan等[ADDINEN.CITE<EndNote><Cite><Author>Wan</Author><Year>2014</Year><RecNum>200</RecNum><DisplayText><styleface="superscript">45</style></DisplayText><record><rec-number>200</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854784">200</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wan,C.</author><author>Regmi,Y.N.</author><author>Leonard,B.M.</author></authors></contributors><auth-address>DepartmentofChemistry,UniversityofWyoming,1000E.UniversityAvenue,Laramie,WY82071(USA)/brianleonard.</auth-address><titles><title>Multiplephasesofmolybdenumcarbideaselectrocatalystsforthehydrogenevolutionreaction</title><secondary-title>AngewChemIntEdEngl</secondary-title></titles><periodical><full-title>AngewChemIntEdEngl</full-title></periodical><pages>6407-10</pages><volume>53</volume><number>25</number><edition>2014/05/16</edition><keywords><keyword>carbides</keyword><keyword>electrocatalysis</keyword><keyword>molybdenum</keyword><keyword>nanocatalysis</keyword><keyword>nanoparticles</keyword></keywords><dates><year>2014</year><pub-dates><date>Jun16</date></pub-dates></dates><isbn>1521-3773(Electronic) 1433-7851(Linking)</isbn><accession-num>24827779</accession-num><urls><related-urls><url>/pubmed/24827779</url></related-urls></urls><electronic-resource-num>10.1002/anie.201402998</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">46</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">wan-</style><styleface="normal"font="default"charset="134"size="100%">不同晶型</style></research-notes></record></Cite></EndNote>45]研究了以上四种不同晶型结构的碳化钼的电催化析氢性能，发现HER活性遵循如下规律：β-Mo2C>γ-MoC>η-MoC>α-MoC1-x，其中，β-Mo2C对催化析氢活性的贡献最大，而γ-MoC表现出最佳稳定性。由于碳化钼灵活多变的化学组成与晶相结构，明确其形成机理对于按需调控其物相来说具有重要的意义。关于碳化钼物相的形成机理，普遍认为这是一个原位渗碳的过程，Chen的团队[ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2013</Year><RecNum>47</RecNum><DisplayText><styleface="superscript">46</style></DisplayText><record><rec-number>47</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1587717300">47</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,W.F.</author><author>Wang,C.H.</author><author>Sasaki,K.</author><author>Marinkovic,N.</author><author>Xu,W.</author><author>Muckerman,J.T.</author><author>Zhu,Y.</author><author>Adzic,R.R.</author></authors></contributors><titles><title>Highlyactiveanddurablenanostructuredmolybdenumcarbideelectrocatalystsforhydrogenproduction</title><secondary-title>EnergyEnvironSci</secondary-title></titles><periodical><full-title>EnergyEnvironSci</full-title></periodical><pages>943</pages><volume>6</volume><number>3</number><section>943</section><dates><year>2013</year></dates><isbn>1754-5692 1754-5706</isbn><urls></urls><electronic-resource-num>10.1039/c2ee23891h</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">47</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Y50-</style><styleface="normal"font="default"charset="134"size="100%">钼酸铵释放氨气</style></research-notes></record></Cite></EndNote>46]证实了这一点。研究以钼酸铵（(NH4)6Mo7O24·4H2O）为钼源，XC-72R炭黑为碳源，利用原位XRD同步监测了从室温25℃到800℃的升温过程中原料逐步转变为碳化钼的相变过程，并结合原料的TG-DTA结果进行分析，提出了钼碳固相反应的机理。首先是钼酸铵的热分解：较低温度（100~350℃）下，(NH4)6Mo7O24·4H2O脱水脱氨形成(NH4)2Mo3O10、(NH4)4Mo8O26等一系列中间化合物，最终形成α-MoO3。其次是α-MoO3与碳发生氧化还原反应（图1.5），碳原子渗入其晶格中，晶格中的氧以CO、CO2的形式扩散到结构以外，于415℃时开始形成MoO2，再形成经过反复的渗碳排氧，碳原子与钼原子重新排列规整，最终在800℃得到稳定的碳化钼。类似的碳化钼形成机理在Kaewpanha等[ADDINEN.CITE<EndNote><Cite><Author>Kaewpanha</Author><Year>2015</Year><RecNum>201</RecNum><DisplayText><styleface="superscript">47</style></DisplayText><record><rec-number>201</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854790">201</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kaewpanha,Malinee</author><author>Guan,Guoqing</author><author>Ma,Yufei</author><author>Hao,Xiaogang</author><author>Zhang,Zhonglin</author><author>Reubroychareon,Prasert</author><author>Kusakabe,Katsuki</author><author>Abudula,Abuliti</author></authors></contributors><titles><title>Hydrogenproductionbysteamreformingof

biomasstarover

biomasscharsupportedmolybdenumcarbidecatalyst</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title><abbr-1>IJHE</abbr-1></periodical><pages>7974-7982</pages><volume>40</volume><number>25</number><section>7974</section><dates><year>2015</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2015.04.068</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">48</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">MC</style><styleface="normal"font="default"charset="134"size="100%">形成过程</style></research-notes></record></Cite></EndNote>47]探讨不同碳化温度对碳化钼物相的影响中被提出，低渗碳温度（600℃）下，XRD仅观察到MoO2，当温度升至700℃时，MoO2的信号峰减弱，并伴随着Mo2C信号开始出现，而纯相Mo2C在800℃时彻底形成。Liang等人[ADDINEN.CITE<EndNote><Cite><Author>Liang</Author><Year>2017</Year><RecNum>202</RecNum><DisplayText><styleface="superscript">48</style></DisplayText><record><rec-number>202</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854795">202</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liang,Pengliang</author><author>Gao,Haifeng</author><author>Yao,Zhiwei</author><author>Jia,Renren</author><author>Shi,Yan</author><author>Sun,Yue</author><author>Fan,Qi</author><author>Wang,Haiyan</author></authors></contributors><titles><title>Simplesynthesisofultrasmallβ-Mo2Candα-MoC1−xnanoparticlesandnewinsightsintotheircatalyticmechanismsfordryreformingofmethane</title><secondary-title>CatalysisScience&Technology</secondary-title></titles><periodical><full-title>CatalysisScience&Technology</full-title></periodical><pages>3312-3324</pages><volume>7</volume><number>15</number><section>3312</section><dates><year>2017</year></dates><isbn>2044-4753 2044-4761</isbn><urls></urls><electronic-resource-num>10.1039/c7cy00708f</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">49-</style><styleface="normal"font="default"charset="134"size="100%">前驱体热解</style><styleface="normal"font="default"size="100%">-</style><styleface="normal"font="default"charset="134"size="100%">气氛</style></research-notes></record></Cite></EndNote>48]采用树脂、钼酸铵为原料，以不同的前驱体制备方法，在不同的还原气体氛围下高温碳化，意外得到不同晶相的碳化钼。在惰性Ar气保护下进行高温煅烧，以离子交换法、浸渍法、机械混合法制备的前驱体分别生成了α-MoC1−x、α-MoC1−x/β-Mo2C和β-Mo2C。然而，在强还原性的H2气体中碳化，所有前驱体均转化为β-Mo2C。其中，不同碳化温度下的XRD表征结果进一步显示，β-Mo2C的形成路线存在两种可能：MoO2→β-Mo2C或MoOx→MoOxCy→β-Mo2C，而α-MoC1−x是通过MoOx→MoOxCy→α-MoC1−x的途径实现的。显然，碳化钼的最终晶相主要取决于前躯体的制备方法和还原气体的种类。同样地，Lee等[ADDINEN.CITE<EndNote><Cite><RecNum>203</RecNum><DisplayText><styleface="superscript">49</style></DisplayText><record><rec-number>203</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854799">203</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors></contributors><titles><title><styleface="normal"font="default"size="100%"><50</style><styleface="normal"font="default"charset="134"size="100%">、调节气氛控制物相</style><styleface="normal"font="default"size="100%">-lee1988.pdf></style></title></titles><dates></dates><urls></urls><research-notes><styleface="normal"font="default"size="100%">50</style><styleface="normal"font="default"charset="134"size="100%">、调节气氛控制物相</style></research-notes></record></Cite></EndNote>49]通过调节渗碳气氛控制过渡金属的物相。正交晶系的MoO3与CH4/H2混合气流在程序升温程序（TPR）后转变为六方晶系的Mo2C，但在MoO3上浸渍了少量铂后，TPR的结果则为立方晶系的α-MoC1−x。此外，通过MoO3与NH3的TPR反应制备的Mo2N，与CH4/H2进一步反应，也能得到α-MoC1−x。图1.5三氧化钼原位渗碳形成碳化钼的过程[ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2013</Year><RecNum>47</RecNum><DisplayText><styleface="superscript">46</style></DisplayText><record><rec-number>47</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1587717300">47</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,W.F.</author><author>Wang,C.H.</author><author>Sasaki,K.</author><author>Marinkovic,N.</author><author>Xu,W.</author><author>Muckerman,J.T.</author><author>Zhu,Y.</author><author>Adzic,R.R.</author></authors></contributors><titles><title>Highlyactiveanddurablenanostructuredmolybdenumcarbideelectrocatalystsforhydrogenproduction</title><secondary-title>EnergyEnvironSci</secondary-title></titles><periodical><full-title>EnergyEnvironSci</full-title></periodical><pages>943</pages><volume>6</volume><number>3</number><section>943</section><dates><year>2013</year></dates><isbn>1754-5692 1754-5706</isbn><urls></urls><electronic-resource-num>10.1039/c2ee23891h</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">47</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Y50-</style><styleface="normal"font="default"charset="134"size="100%">钼酸铵释放氨气</style></research-notes></record></Cite></EndNote>46]Figure1.5InsitucarburizingprocessofMoO3formingMo2C[ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2013</Year><RecNum>47</RecNum><DisplayText><styleface="superscript">46</style></DisplayText><record><rec-number>47</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1587717300">47</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,W.F.</author><author>Wang,C.H.</author><author>Sasaki,K.</author><author>Marinkovic,N.</author><author>Xu,W.</author><author>Muckerman,J.T.</author><author>Zhu,Y.</author><author>Adzic,R.R.</author></authors></contributors><titles><title>Highlyactiveanddurablenanostructuredmolybdenumcarbideelectrocatalystsforhydrogenproduction</title><secondary-title>EnergyEnvironSci</secondary-title></titles><periodical><full-title>EnergyEnvironSci</full-title></periodical><pages>943</pages><volume>6</volume><number>3</number><section>943</section><dates><year>2013</year></dates><isbn>1754-5692 1754-5706</isbn><urls></urls><electronic-resource-num>10.1039/c2ee23891h</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">47</style><styleface="normal"font="default"charset="134"size="100%">、</style><styleface="normal"font="default"size="100%">Y50-</style><styleface="normal"font="default"charset="134"size="100%">钼酸铵释放氨气</style></research-notes></record></Cite></EndNote>46].表1.2不同制备方法得到的样品的物相[ADDINEN.CITE<EndNote><Cite><Author>Liang</Author><Year>2017</Year><RecNum>202</RecNum><DisplayText><styleface="superscript">48</style></DisplayText><record><rec-number>202</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854795">202</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liang,Pengliang</author><author>Gao,Haifeng</author><author>Yao,Zhiwei</author><author>Jia,Renren</author><author>Shi,Yan</author><author>Sun,Yue</author><author>Fan,Qi</author><author>Wang,Haiyan</author></authors></contributors><titles><title>Simplesynthesisofultrasmallβ-Mo2Candα-MoC1−xnanoparticlesandnewinsightsintotheircatalyticmechanismsfordryreformingofmethane</title><secondary-title>CatalysisScience&Technology</secondary-title></titles><periodical><full-title>CatalysisScience&Technology</full-title></periodical><pages>3312-3324</pages><volume>7</volume><number>15</number><section>3312</section><dates><year>2017</year></dates><isbn>2044-4753 2044-4761</isbn><urls></urls><electronic-resource-num>10.1039/c7cy00708f</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">49-</style><styleface="normal"font="default"charset="134"size="100%">前驱体热解</style><styleface="normal"font="default"size="100%">-</style><styleface="normal"font="default"charset="134"size="100%">气氛</style></research-notes></record></Cite></EndNote>48]Table1.2Thephasestructureofsamplesobtainedbyvariousmethods[ADDINEN.CITE<EndNote><Cite><Author>Liang</Author><Year>2017</Year><RecNum>202</RecNum><DisplayText><styleface="superscript">48</style></DisplayText><record><rec-number>202</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854795">202</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liang,Pengliang</author><author>Gao,Haifeng</author><author>Yao,Zhiwei</author><author>Jia,Renren</author><author>Shi,Yan</author><author>Sun,Yue</author><author>Fan,Qi</author><author>Wang,Haiyan</author></authors></contributors><titles><title>Simplesynthesisofultrasmallβ-Mo2Candα-MoC1−xnanoparticlesandnewinsightsintotheircatalyticmechanismsfordryreformingofmethane</title><secondary-title>CatalysisScience&Technology</secondary-title></titles><periodical><full-title>CatalysisScience&Technology</full-title></periodical><pages>3312-3324</pages><volume>7</volume><number>15</number><section>3312</section><dates><year>2017</year></dates><isbn>2044-4753 2044-4761</isbn><urls></urls><electronic-resource-num>10.1039/c7cy00708f</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">49-</style><styleface="normal"font="default"charset="134"size="100%">前驱体热解</style><styleface="normal"font="default"size="100%">-</style><styleface="normal"font="default"charset="134"size="100%">气氛</style></research-notes></record></Cite></EndNote>48].温度离子交换法浸渍法机械混合法ArH2ArH2ArH2350℃非晶非晶非晶MoO2MoO2MoO2500℃非晶非晶非晶MoO2MoO2MoO2700℃MoOxCyβ-Mo2C,MoOxCyMoO2,MoOxCyβ-Mo2C,MoOxCyMoO2,MoOxCyMoOxCy,β-Mo2C900℃α-MoC1−xβ-Mo2Cβ-Mo2C,α-MoC1−xβ-Mo2Cβ-Mo2Cβ-Mo2C在上述研究中，碳化钼的形成途径主要是通过生成中间钼氧化物再继续碳化得到的，而在ZheLv等人[ADDINEN.CITE<EndNote><Cite><Author>Lv</Author><Year>2017</Year><RecNum>204</RecNum><DisplayText><styleface="superscript">50</style></DisplayText><record><rec-number>204</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854804">204</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lv,Zhe</author><author>Tahir,Muhammad</author><author>Lang,Xuewei</author><author>Yuan,Gang</author><author>Pan,Lun</author><author>Zhang,Xiangwen</author><author>Zou,Ji-Jun</author></authors></contributors><titles><title>Well-dispersedmolybdenumnitridesonanitrogen-dopedcarbonmatrixforhighlyefficienthydrogenevolutioninalkalinemedia</title><secondary-title>J.Mater.Chem.A</secondary-title></titles><periodical><full-title>J.Mater.Chem.A</full-title></periodical><pages>20932-20937</pages><volume>5</volume><number>39</number><section>20932</section><dates><year>2017</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c7ta06981b</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">51</style><styleface="normal"font="default"charset="134"size="100%">、氮化钼转变为碳化钼</style></research-notes></record></Cite></EndNote>50]的研究中报道了不一样的转化路径。研究以富氮的三聚氰胺和三氧化钼为前体，通过溶液蒸发法获取均匀的前驱体，并在Ar气中进行高温煅烧。较低温度下（550℃），体系中出现MoO2与Mo2N的混合相，600℃时，只观察到Mo2N。继续升高温度到650℃时，β-Mo2C开始形成，表明随着温度的升高，MoO3被还原为MoO2，然后转化为Mo2N，Mo2N在更高的温度下转化为Mo2C，这种转变是由碳化物逐渐占据氮化物晶格的拓扑反应引起的，即N原子扩散出去，C原子渗入取代N原子，而金属钼原子保持静止。本课题组曾在构建Mo2C/Mo2N异质结构的工作中，也发现了物相随着温度发生转变的现象：γ-Mo2N（600℃）→Mo2C/Mo2N（700℃）→β-Mo2C（800℃）[ADDINEN.CITE<EndNote><Cite><Author>WeiwenWang</Author><Year>2019</Year><RecNum>151</RecNum><DisplayText><styleface="superscript">51</style></DisplayText><record><rec-number>151</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1595404319">151</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>WeiwenWang,</author><author>CanLiua,</author><author>DaliZhou,</author><author>LeiYang,</author><author>JiabeiZhou,</author><author>DongruiYang</author></authors></contributors><titles><title>In-situsynthesisofcoupledmolybdenumcarbideandmolybdenumnitrideaselectrocatalystforhydrogenevolutionreaction</title><secondary-title>JAlloyCompd</secondary-title></titles><periodical><full-title>JAlloyCompd</full-title></periodical><pages>230-239</pages><volume>792</volume><dates><year>2019</year></dates><urls></urls><electronic-resource-num>10.1016/j.jallcom.2019.03.397</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">52</style><styleface="normal"font="default"charset="134"size="100%">、碳谱参考</style></research-notes></record></Cite></EndNote>51]。这表明在形成碳化钼物相的过程中，根据反应条件、制备方法、使用原料的不同，氧化钼不是唯一的中间过渡相，碳化钼也可以通过氮化钼低温相在较高的温度下转化得来。因此，碳化钼的形成机理需要结合具体情况具体分析，不能同一而论。碳化钼的制备方法起初，碳化钼的制备依靠高温碳化来实现，即在高于1000℃的高温下直接将钼碳化，这种方法得到的碳化钼颗粒大，比表面积小，形貌尺寸难以控制，不利于合成高性能的碳化钼催化剂。要想提高材料的析氢催化活性，必须具有较小的颗粒尺寸、较大的比表面积、充分暴露的足够多的活性位点，因此选择有效的材料制备方法尤为重要。（1）程序升温还原法（Temperatureprogrammedreductionmethod,TPR）TPR法是指以MoO2或MoO3作为碳化前体，烃类气体如CH4、C2H6、C3H8的高温裂解物作为碳源，在通入H2作为还原气的缓慢升温过程中实现材料的高温碳化。其中，热处理条件取决于烃类分子链断裂的难易程度，容易断裂的长链烷烃对应的碳化温度低于结构较稳定的短链烷烃[ADDINEN.CITE<EndNote><Cite><RecNum>205</RecNum><DisplayText><styleface="superscript">52</style></DisplayText><record><rec-number>205</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854808">205</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors></contributors><titles><title><styleface="normal"font="default"size="100%"><53</style><styleface="normal"font="default"charset="134"size="100%">、碳化钼催化剂的制备及应用研究进展</style><styleface="normal"font="default"size="100%">_</style><styleface="normal"font="default"charset="134"size="100%">看图王</style><styleface="normal"font="default"size="100%">.pdf></style></title></titles><dates></dates><urls></urls><research-notes><styleface="normal"font="default"size="100%">53</style><styleface="normal"font="default"charset="134"size="100%">、碳化钼催化剂的制备及应用</style></research-notes></record></Cite></EndNote>52]。采用TPR法可以按需调控原料配比、控制反应条件来制备不同形貌、晶型、孔道结构的碳化钼。在Roohi等人[ADDINEN.CITE<EndNote><Cite><Author>Roohi</Author><Year>2016</Year><RecNum>206</RecNum><DisplayText><styleface="superscript">53</style></DisplayText><record><rec-number>206</rec-number><foreign-keys><keyapp="EN"db-id="sdaasdwx8pzdd9epw0fxvz2e2tsprtp0vatx"timestamp="1614854816">206</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Roohi,Parham</author><author>Alizadeh,Reza</author><author>Fatehifar,Esmaeil</author></authors></contributors><titles><title>Thermodynamicstudyandmethanothermaltemperature-programmedreactionsynthesisofmolybdenumcarbide</title><secondary-title>InternationalJournalofMinerals,Metallurgy,andMaterials</secondary-title></titles><periodical><full-title>InternationalJournalofMinerals,Metallurgy,andMaterials</full-title></periodical><pages>339-347</pages><volume>23</volume><number>3</number><section>339</section><dates><year>2016</year></dates><isbn>1674-4799 1869-103X</isbn><urls></urls><electronic-resource-num>10.1007/s12613-016-1243-y</electronic-resource-num><research-notes><styleface="normal"font="default"size="100%">5