改善鎂/氫化鎂水解放氫性能研究進(jìn)展基金項(xiàng)目：國家自然科學(xué)基金資助項(xiàng)目（基金項(xiàng)目：國家自然科學(xué)基金資助項(xiàng)目（51771112）NationalScienceFoundation(No.51771112)楊波，鄒建新，曾小勤，丁文江（上海交通大學(xué)材料科學(xué)與工程學(xué)院，上海200240）摘要為了提高M(jìn)g/MgH2水解產(chǎn)氫性能，科研人員做了大量的改進(jìn)工作。本文概述了Mg/MgH2水解產(chǎn)氫過程中遇到的問題，以及提高水解反應(yīng)動(dòng)力學(xué)的方法：一是增大Mg/MgH2的比表面積，二是打破水解過程中產(chǎn)生的Mg(OH)2保護(hù)層對(duì)水解的限制。因此可以通過降低粉末尺寸、在溶液中添加不同催化劑（酸、鹽等）和復(fù)合具有催化作用的第二相（金屬氧化物、氯化物、金屬氫化物、金屬、石墨等）來改善水解性能。重點(diǎn)闡述了催化劑對(duì)Mg/MgH2水解性能的影響及作用機(jī)理，并提出了一些建議與看法。關(guān)鍵字：鎂；氫化鎂；水解；催化；氫氣中圖分類號(hào)：TK91文獻(xiàn)標(biāo)識(shí)碼：ARecentadvancesinimprovingthehydrolysisperformanceofmagnesium/magnesiumhydride200240,ChinaAbstractInordertoimprovethehydrolysisperformanceofMg/MgH2,researchershavedonelotsofimprovementwork.TheproblemsinthehydrogenproductionfromMg/MgH2hydrolysisandthemethodstoincreasethekineticsofhydrolysisreactionaresummarizedinthispaper.First,increasethespecificsurfaceareaofMg/MgH2.Second,breakthelimitationofMg(OH)2protectivelayerproducedinthehydrolysisprocess.Therefore,thehydrolysisperformancecanbeimprovedbyreducingthepowdersize,addingdifferentcatalysts(acids,salts,etc.)intothesolutionandcompositingcatalyticsecondphases(metaloxides,chlorides,metalhydrides,metals,graphite,etc.).TheeffectsandmechanismsofcatalystsonthehydrolysisperformanceofMg/MgH2arehighlighted.Furthermore,somesuggestionsandideasareproposed.Keywordsmagnesium,magnesiumhydride,hydrolysis,catalyze,hydrogen由于環(huán)境污染及能源緊缺問題日益嚴(yán)重，發(fā)展新型清潔高效的新能源、新材料成為中國制造2025的重大戰(zhàn)略目標(biāo)ADDINEN.CITE<EndNote><Cite><Author>氣候變化研究進(jìn)展</Author><Year>2019</Year><RecNum>447</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>447</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550328289">447</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>姜克雋%J氣候變化研究進(jìn)展</author></authors></contributors><titles><title>一個(gè)強(qiáng)有力的2050碳減排目標(biāo)將非常有利于中國的社會(huì)經(jīng)濟(jì)發(fā)展</title></titles><pages>103-106</pages><volume>15</volume><number>1</number><dates><year>2019</year></dates><isbn>1673-1719</isbn><urls></urls></record></Cite></EndNote>[1]。氫氣具有清潔、環(huán)保、可再生、高能量密度等特點(diǎn)ADDINEN.CITE<EndNote><Cite><Author>伊文婧</Author><Year>2018</Year><RecNum>449</RecNum><DisplayText><styleface="superscript">[2]</style></DisplayText><record><rec-number>449</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550328993">449</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>伊文婧</author><author>梁琦</author><author>裴慶冰%J環(huán)境保護(hù)</author></authors></contributors><titles><title>氫能促進(jìn)我國能源系統(tǒng)清潔低碳轉(zhuǎn)型的應(yīng)用及進(jìn)展</title></titles><pages>30-34</pages><volume>2</volume><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[2]，其產(chǎn)熱量是汽油的3倍ADDINEN.CITE<EndNote><Cite><Author>王朔</Author><Year>2017</Year><RecNum>450</RecNum><DisplayText><styleface="superscript">[3]</style></DisplayText><record><rec-number>450</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550329138">450</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>王朔</author><author>張軍%J儲(chǔ)能科學(xué)與技術(shù)</author></authors></contributors><titles><title>我國制氫技術(shù)發(fā)展態(tài)勢(shì)與技術(shù)路線研究——基于專利分析</title></titles><pages>1</pages><dates><year>2017</year></dates><isbn>2095-4239</isbn><urls></urls></record></Cite></EndNote>[3]，在新能源領(lǐng)域具有廣泛的應(yīng)用前景。然而，制氫和儲(chǔ)氫技術(shù)嚴(yán)重限制了氫能的發(fā)展與應(yīng)用，慶幸的是科研人員發(fā)現(xiàn)鎂具有優(yōu)異的儲(chǔ)氫性能和簡單的制氫工藝，是氫能發(fā)展領(lǐng)域最有潛力的輕金屬材料之一。鎂是地球上儲(chǔ)量最豐富的輕合金元素之一ADDINEN.CITE<EndNote><Cite><Author>Jain</Author><Year>2010</Year><RecNum>175</RecNum><DisplayText><styleface="superscript">[4]</style></DisplayText><record><rec-number>175</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540885560">175</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jain,I.P.</author><author>Lal,Chhagan</author><author>Jain,Ankur</author></authors></contributors><titles><title>HydrogenstorageinMg:Amostpromisingmaterial</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>5133-5144</pages><volume>35</volume><number>10</number><section>5133</section><dates><year>2010</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2009.08.088</electronic-resource-num></record></Cite></EndNote>[4]，我國的鎂儲(chǔ)量十分豐富，居世界第二位。鎂不僅具有價(jià)格低廉、密度低（1.8gcm-3）、比強(qiáng)度高等優(yōu)點(diǎn)ADDINEN.CITE<EndNote><Cite><Author>孟天宇</Author><Year>2016</Year><RecNum>453</RecNum><DisplayText><styleface="superscript">[5]</style></DisplayText><record><rec-number>453</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550383076">453</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>孟天宇</author><author>張濤</author><author>李月</author><author>劉悅</author><author>朱晶</author><author>王忠軍%J遼寧科技大學(xué)學(xué)報(bào)</author></authors></contributors><titles><title>Mg-Al和Mg-Li鎂合金板在NaCl水溶液中的腐蝕行為</title></titles><pages>446-454</pages><volume>39</volume><number>6</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[5]，而且儲(chǔ)氫容量高達(dá)7.6wt.%，超過了美國能源部（DOE）5.5wt.%的要求（2025年目標(biāo)、終極目標(biāo)是6.5wt.%）ADDINEN.CITE<EndNote><Cite><Author>李璐伶</Author><Year>2018</Year><RecNum>451</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>451</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550329545">451</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>李璐伶</author><author>樊栓獅</author><author>陳秋雄</author><author>楊光</author><author>溫永剛%J儲(chǔ)能科學(xué)與技術(shù)</author></authors></contributors><titles><title>儲(chǔ)氫技術(shù)研究現(xiàn)狀及展望</title></titles><pages>586-594</pages><volume>7</volume><number>4</number><dates><year>2018</year></dates><isbn>2095-4239</isbn><urls></urls></record></Cite></EndNote>[6]，是金屬儲(chǔ)氫材料中的佼佼者。Mg氫化后得到的MgH2可以通過熱分解和水解兩種方式來制備氫氣，但熱分解的放氫焓變較高（74.5kJmol-1），導(dǎo)致需要在350℃以上才能分解放出氫氣。與此相反，水解在室溫下就能進(jìn)行，放氫量為15.2wt.%（不把水計(jì)算在內(nèi)），是熱分解放氫量的2倍，水解反應(yīng)方程式可見式（1）ADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2015</Year><RecNum>114</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>114</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540195312">114</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Minghong</author><author>Ouyang,Liuzhang</author><author>Wang,Hui</author><author>Liu,Jiangwen</author><author>Zhu,Min</author></authors></contributors><titles><title>HydrogengenerationbyhydrolysisofMgH2andenhancedkineticsperformanceofammoniumchlorideintroducing</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>6145-6150</pages><volume>40</volume><number>18</number><section>6145</section><dates><year>2015</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2015.03.058</electronic-resource-num></record></Cite></EndNote>[7]。與MgH2相似，Mg也可以水解放出氫氣，反應(yīng)方程式如（2）所示ADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2017</Year><RecNum>239</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>239</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540888952">239</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Minghong</author><author>Ouyang,Liuzhang</author><author>Ye,Jianshan</author><author>Liu,Jiangwen</author><author>Yao,Xiangdong</author><author>Wang,Hui</author><author>Shao,Huaiyu</author><author>Zhu,Min</author></authors></contributors><titles><title>HydrogengenerationviahydrolysisofmagnesiumwithseawaterusingMo,MoO2,MoO3andMoS2ascatalysts</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>8566-8575</pages><volume>5</volume><number>18</number><section>8566</section><dates><year>2017</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c7ta02457f</electronic-resource-num></record></Cite></EndNote>[8]。雖然水解反應(yīng)具有反應(yīng)條件溫和、放氫量大等優(yōu)點(diǎn)，但水解副產(chǎn)物Mg(OH)2附在MgH2的表面嚴(yán)重限制了水解反應(yīng)的進(jìn)行ADDINEN.CITE<EndNote><Cite><Author>Tegel</Author><Year>2017</Year><RecNum>110</RecNum><DisplayText><styleface="superscript">[9]</style></DisplayText><record><rec-number>110</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1536930791">110</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tegel,Marcus</author><author>Sch?ne,Sebastian</author><author>Kieback,Bernd</author><author>R?ntzsch,Lars</author></authors></contributors><titles><title>AnefficienthydrolysisofMgH2-basedmaterials</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>2167-2176</pages><volume>42</volume><number>4</number><section>2167</section><dates><year>2017</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2016.09.084</electronic-resource-num></record></Cite></EndNote>[9]。MgH2+2H2O→Mg(OH)2+2H2↑,?H=-277kJmol-1（1）Mg+2H2O→Mg(OH)2+H2↑,?H=-384kJmol-1（2）為了打破Mg(OH)2保護(hù)層對(duì)Mg/MgH2水解產(chǎn)氫的限制，改善水解反應(yīng)的動(dòng)力學(xué)，提升水解反應(yīng)速度和水解放氫量，科研工作者做了大量改善工作，期望Mg/MgH2水解產(chǎn)氫能夠在生產(chǎn)生活方面（尤其在新能源汽車領(lǐng)域）得到廣泛的應(yīng)用。1降低粉末尺寸降低Mg/MgH2的顆粒尺寸能夠增大比表面積，增大Mg/MgH2與水的接觸面積，提高水解反應(yīng)動(dòng)力學(xué)。目前降低顆粒顆粒尺寸的主要方法有球磨法和直流電弧等離子體法等。Hu等人ADDINEN.CITE<EndNote><Cite><Author>Hu</Author><Year>2005</Year><RecNum>379</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>379</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1544754354">379</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hu,Lian-Xi</author><author>Wang,Er-De%JTransactionsofNonferrousMetalsSocietyofChina</author></authors></contributors><titles><title>HydrogengenerationviahydrolysisofnanocrystallineMgH2andMgH2-basedcomposites</title></titles><pages>965-970</pages><volume>15</volume><number>5</number><dates><year>2005</year></dates><isbn>1003-6326</isbn><urls></urls></record></Cite></EndNote>[10]使用球磨法研磨MgH2以達(dá)到降低顆粒尺寸的目的。球磨15h后發(fā)現(xiàn)MgH2的顆粒尺寸減小到了13nm。由于球磨增加了比表面積，具有獨(dú)特的納米晶體結(jié)構(gòu)，使得球磨后的MgH2比商業(yè)的多晶MgH2具有更好的動(dòng)力學(xué)性能，水解放氫量得到了顯著的提升。在70min內(nèi)水解產(chǎn)氫量由理論值的7.5%增加到了25%。球磨法所使用的器械雖然價(jià)格低廉，但生產(chǎn)效率低下，只適合實(shí)驗(yàn)室小批量生產(chǎn)，無法滿足工業(yè)大批量生產(chǎn)的需求。直流電弧等離子體法相對(duì)于球磨法，制備的粉末顆粒更加均勻細(xì)膩，生產(chǎn)效率高，適合大批量工業(yè)生產(chǎn)，具有更大的應(yīng)用前景。Mao等ADDINEN.CITE<EndNote><Cite><Author>Mao</Author><Year>2017</Year><RecNum>115</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>115</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540522960">115</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mao,Jianfeng</author><author>Zou,Jianxin</author><author>Lu,Chong</author><author>Zeng,Xiaoqin</author><author>Ding,Wenjiang</author></authors></contributors><titles><title>Hydrogenstorageandhydrolysispropertiesofcore-shellstructuredMg-MFx(M=V,Ni,LaandCe)nano-compositespreparedbyarcplasmamethod</title><secondary-title>JournalofPowerSources</secondary-title></titles><periodical><full-title>JournalofPowerSources</full-title></periodical><pages>131-142</pages><volume>366</volume><section>131</section><dates><year>2017</year></dates><isbn>03787753</isbn><urls></urls><electronic-resource-num>10.1016/j.jpowsour.2017.09.015</electronic-resource-num></record></Cite></EndNote>[11]用直流電弧等離子體法制備了納米Mg顆粒，氫化處理后，在室溫下、0.1mol/LMgCl2水溶液中水解，發(fā)現(xiàn)水解放氫量與商業(yè)購買的MgH2相比是商業(yè)MgH2的7倍左右，并且水解放氫速度遠(yuǎn)超商業(yè)MgH2。2在溶液中添加酸和鹽2.1在溶液中添加酸在溶液中添加酸，能夠破壞Mg(OH)2保護(hù)層，提升水解動(dòng)力學(xué)。Tayeh等ADDINEN.CITE<EndNote><Cite><Author>Tayeh</Author><Year>2014</Year><RecNum>244</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>244</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540888983">244</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tayeh,T.</author><author>Awad,A.S.</author><author>Nakhl,M.</author><author>Zakhour,M.</author><author>Silvain,J.F.</author><author>Bobet,J.L.</author></authors></contributors><titles><title>Productionofhydrogenfrommagnesiumhydrideshydrolysis</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>3109-3117</pages><volume>39</volume><number>7</number><section>3109</section><dates><year>2014</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2013.12.082</electronic-resource-num></record></Cite></EndNote>[12]研究了不同種類強(qiáng)酸對(duì)MgH2水解性能的影響，發(fā)現(xiàn)在PH=2酸溶液中，H2SO4溶液中的水解放氫量和放氫速度均高于在HCl和HNO3，他們認(rèn)為這是由于H2SO4是二元酸，且H2SO4的生成焓高于Mg(OH)2所導(dǎo)致的。這也就說明H2SO4分解出H+的過程中會(huì)放出比HCl和HNO3更多的熱量，這些熱量對(duì)水解動(dòng)力學(xué)的提升具有促進(jìn)的作用。然而，由于強(qiáng)酸腐蝕性較強(qiáng)、嚴(yán)重污染壞境且水解放出的氫氣大部分來自強(qiáng)酸的H+，實(shí)際應(yīng)用價(jià)值較小。Kushch等ADDINEN.CITE<EndNote><Cite><Author>Kushch</Author><Year>2011</Year><RecNum>260</RecNum><DisplayText><styleface="superscript">[13]</style></DisplayText><record><rec-number>260</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1541078623">260</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kushch,S.D.</author><author>Kuyunko,N.S.</author><author>Nazarov,R.S.</author><author>Tarasov,B.P.</author></authors></contributors><titles><title>Hydrogen-generatingcompositionsbasedonmagnesium</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>1321-1325</pages><volume>36</volume><number>1</number><section>1321</section><dates><year>2011</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2010.06.115</electronic-resource-num></record></Cite></EndNote>[13]認(rèn)為使用有機(jī)弱酸，比如檸檬酸，作為添加劑，具有較好的經(jīng)濟(jì)效益，由于檸檬酸是弱酸，能夠及時(shí)補(bǔ)充溶液中消耗掉的H+，從而使水解放氫反應(yīng)更加穩(wěn)定、更加安全。Jen等ADDINEN.CITE<EndNote><Cite><Author>Jen</Author><Year>2016</Year><RecNum>458</RecNum><DisplayText><styleface="superscript">[14]</style></DisplayText><record><rec-number>458</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550387918">458</key></foreign-keys><ref-typename="ConferenceProceedings">10</ref-type><contributors><authors><author>Jen,Tien-Chien</author><author>Adeniran,Joshua</author><author>Akinlabi,Esther</author><author>Chao,Chung-Hsing</author><author>Ho,Yen-Hsi</author><author>DeKoker,Johan</author></authors></contributors><titles><title>Hydrogengenerationfromaceticacidcatalyzedmagnesiumhydrideusinganon-demandhydrogenreactor</title><secondary-title>ASME2016InternationalMechanicalEngineeringCongressandExposition</secondary-title></titles><pages>V06AT08A034-V06AT08A034</pages><dates><year>2016</year></dates><publisher>AmericanSocietyofMechanicalEngineers</publisher><urls></urls></record></Cite></EndNote>[14]研究了醋酸濃度、溫度和MgH2的含量對(duì)放氫性能的影響，發(fā)現(xiàn)：1）放氫速度隨著醋酸濃度的增高先增加后減小，當(dāng)醋酸濃度為60wt.%時(shí)放氫速度最高；2）溫度（30℃~60℃）對(duì)放氫速度與放氫量的影響不大；3）MgH2的含量對(duì)放氫量起到?jīng)Q定性的作用。由此可見，在室溫下使用60wt.%的醋酸就能使MgH2達(dá)到良好的放氫效果。Jen等之所以得出這樣的結(jié)論是因?yàn)殡S著醋酸濃度的增高，溶液中H+的濃度雖然在逐漸增高但H+的總量卻在先增加后減少，所以在濃度超過60wt.%時(shí)，溶液中H+總量成了限制水解快慢的因素。在他們的實(shí)驗(yàn)中由于使用的醋酸濃度較高，反應(yīng)速度極快，使得溫度的影響變得不明顯，并且由于使用的醋酸是過量的所以添加的MgH2的質(zhì)量成了放氫總量的限制性因素?？傊?，醋酸在提升Mg/MgH2水解性能方面是一種相對(duì)較好的催化劑。2.2在溶液中加入鹽在溶液中加入酸，即使是弱酸也很難使水解產(chǎn)生的H2全部來自于H2O，然而在溶液中加入鹽卻能夠達(dá)到這一點(diǎn)。一般認(rèn)為，Mg/MgH2在酸式鹽溶液的水解效果高于其他鹽溶液。酸式鹽提供的酸性環(huán)境與弱酸提供的酸性環(huán)境在破壞Mg(OH)2保護(hù)層方面具有異曲同工之妙。Huang等ADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2015</Year><RecNum>114</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>114</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540195312">114</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Minghong</author><author>Ouyang,Liuzhang</author><author>Wang,Hui</author><author>Liu,Jiangwen</author><author>Zhu,Min</author></authors></contributors><titles><title>HydrogengenerationbyhydrolysisofMgH2andenhancedkineticsperformanceofammoniumchlorideintroducing</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>6145-6150</pages><volume>40</volume><number>18</number><section>6145</section><dates><year>2015</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2015.03.058</electronic-resource-num></record></Cite></EndNote>[7]發(fā)現(xiàn)NH4Cl能夠顯著地提高M(jìn)gH2水解的動(dòng)力學(xué)性能。水解放氫量和激活能如表（1）所示。從表中數(shù)據(jù)可以看出，4.5wt.%的NH4Cl水溶液顯著降低了MgH2的水解激活能，并極大提高了水解放氫量和水解放氫速度。與NH4Cl相似，AlCl3也可以提高M(jìn)g/MgH2的水解性能ADDINEN.CITE<EndNote><Cite><Author>Gan</Author><Year>2018</Year><RecNum>454</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>454</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1550383563">454</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Gan,Deyu</author><author>Liu,Yana</author><author>Zhang,Jiguang</author><author>Zhang,Yao</author><author>Cao,Chuntao</author><author>Zhu,Yunfeng</author><author>Li,Liquan%JInternationalJournalofHydrogenEnergy</author></authors></contributors><titles><title>KineticperformanceofhydrogengenerationenhancedbyAlCl3viahydrolysisofMgH2preparedbyhydridingcombustionsynthesis</title></titles><pages>10232-10239</pages><volume>43</volume><number>22</number><dates><year>2018</year></dates><isbn>0360-3199</isbn><urls></urls></record></Cite></EndNote>[15]。表1MgH2在不同濃度NH4Cl水溶液中水解不同時(shí)間的放氫量和水解激活能Table1ThehydrogenyieldsandactivationenergiesofhydrolysisofMgH2indifferentconcentrationsofNH4Clsolutionindifferenttime.NH4Cl溶液濃度5min(mLg-1)10min(mLg-1)30min(mLg-1)激活能（kJmol-1H2）去離子水11417420958.060.5wt.%50164198050.864.5wt.%13101604166030.37（全英表格）TheconcentrationsofNH4Clsolution5min(mLg-1)10min(mLg-1)30min(mLg-1)Activationenergies(kJmol-1H2)deionizedwater11417420958.060.5wt.%50164198050.864.5wt.%13101604166030.37Zhao等ADDINEN.CITE<EndNote><Cite><Author>Zhao</Author><Year>2012</Year><RecNum>131</RecNum><DisplayText><styleface="superscript">[16]</style></DisplayText><record><rec-number>131</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540792113">131</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhao,Z.</author><author>Zhu,Y.</author><author>Li,L.</author></authors></contributors><auth-address>CollegeofMaterialsScienceandEngineering,NanjingUniversityofTechnology,5XinmofanRoad,Nanjing,Jiangsu,PRChina.</auth-address><titles><title>EfficientcatalysisbyMgCl2inhydrogengenerationviahydrolysisofMg-basedhydridepreparedbyhydridingcombustionsynthesis</title><secondary-title>ChemCommun(Camb)</secondary-title></titles><periodical><full-title>ChemCommun(Camb)</full-title></periodical><pages>5509-11</pages><volume>48</volume><number>44</number><edition>2012/04/28</edition><dates><year>2012</year><pub-dates><date>Jun4</date></pub-dates></dates><isbn>1364-548X(Electronic) 1359-7345(Linking)</isbn><accession-num>22538836</accession-num><urls><related-urls><url>/pubmed/22538836</url></related-urls></urls><electronic-resource-num>10.1039/c2cc32353b</electronic-resource-num></record></Cite></EndNote>[16]發(fā)現(xiàn)MgCl2對(duì)Mg基氫化物的水解起到了顯著的催化作用。Mg基氫化物在30℃去離子水中水解3min的水解放氫量為192mLg-1，而在0.5mol/LMgCl2水溶液中水解3min的放氫量達(dá)到了927mLg-1，將近去離子水中的5倍，并且當(dāng)反應(yīng)后的溶液被循環(huán)使用9次后，30min的水解放氫量人仍高達(dá)1600mLg-1，轉(zhuǎn)化率為94%。他們認(rèn)為這是由于MgCl2溶液提供的酸性環(huán)境導(dǎo)致MgH2的水解放氫量和水解速率得到了明顯的提升。但Chen等ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2014</Year><RecNum>132</RecNum><DisplayText><styleface="superscript">[17]</style></DisplayText><record><rec-number>132</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540793143">132</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Jun</author><author>Fu,He</author><author>Xiong,Yifu</author><author>Xu,Jinrong</author><author>Zheng,Jie</author><author>Li,Xingguo</author></authors></contributors><titles><title>MgCl2promotedhydrolysisofMgH2nanoparticlesforhighlyefficientH2generation</title><secondary-title>NanoEnergy</secondary-title></titles><periodical><full-title>NanoEnergy</full-title></periodical><pages>337-343</pages><volume>10</volume><section>337</section><dates><year>2014</year></dates><isbn>22112855</isbn><urls></urls><electronic-resource-num>10.1016/j.nanoen.2014.10.002</electronic-resource-num></record></Cite></EndNote>[17]認(rèn)為這是因?yàn)镸gH2水解過程中產(chǎn)生的OH-與溶液中的Mg2+相結(jié)合在溶液中形成Mg(OH)2懸浮顆粒并沉淀下來，而不是在MgH2表面形成Mg(OH)2保護(hù)層的緣故。MgH2水解產(chǎn)生的Mg2+補(bǔ)充了溶液中損失的Mg2+，從而使溶液中的Mg2+處于平衡的狀態(tài)，反應(yīng)示意圖如圖1所示。由于溶液中Mg2+的濃度不變，所以反應(yīng)后的溶液能夠反復(fù)使用，這也是MgCl2比NH4Cl和AlCl3具有更好應(yīng)用前景的原因。圖1MgH2在去離子水中（a）和0.5mol/LMgCl2水溶液中（b）水解反應(yīng)示意圖ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2014</Year><RecNum>132</RecNum><DisplayText><styleface="superscript">[17]</style></DisplayText><record><rec-number>132</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540793143">132</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Jun</author><author>Fu,He</author><author>Xiong,Yifu</author><author>Xu,Jinrong</author><author>Zheng,Jie</author><author>Li,Xingguo</author></authors></contributors><titles><title>MgCl2promotedhydrolysisofMgH2nanoparticlesforhighlyefficientH2generation</title><secondary-title>NanoEnergy</secondary-title></titles><periodical><full-title>NanoEnergy</full-title></periodical><pages>337-343</pages><volume>10</volume><section>337</section><dates><year>2014</year></dates><isbn>22112855</isbn><urls></urls><electronic-resource-num>10.1016/j.nanoen.2014.10.002</electronic-resource-num></record></Cite></EndNote>[17]Fig.1SchematicdiagramofhydrolysisreactionofMgH2indeionizedwater(a)and0.5mol/LMgCl2aqueoussolution(b)[17]Kravchenko等ADDINEN.CITE<EndNote><Cite><Author>Kravchenko</Author><Year>2014</Year><RecNum>386</RecNum><DisplayText><styleface="superscript">[18]</style></DisplayText><record><rec-number>386</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1544794118">386</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kravchenko,OV</author><author>Sevastyanova,LG</author><author>Urvanov,SA</author><author>Bulychev,BM%JInternationalJournalofHydrogenEnergy</author></authors></contributors><titles><title>FormationofhydrogenfromoxidationofMg,MgalloysandmixturewithNi,Co,CuandFeinaqueoussaltsolutions</title></titles><pages>5522-5527</pages><volume>39</volume><number>11</number><dates><year>2014</year></dates><isbn>0360-3199</isbn><urls></urls></record></Cite></EndNote>[18]機(jī)械球磨Mg粉后在不同鹽溶液中測(cè)試Mg的產(chǎn)氫率，結(jié)果如圖2所示。在溶液中加入NH4Cl、NaCl、MgCl2、KCl、CaCl2對(duì)Mg水解產(chǎn)氫具有明顯的提升作用，而NaBr、KBr、NaI的提升作用不明顯。這是因?yàn)槌岁栯x子的作用（NH4+提供的酸性環(huán)境、Mg2+的催化作用）外，Cl-相比于Br-和I-更加有利于Mg在水中的腐蝕。由此可見，陰離子Cl-對(duì)Mg(OH)2保護(hù)膜具有一定的破壞作用。圖21gMg在分別在30mL堿金屬、堿土金屬鹵化物和氯化銨水溶液中的產(chǎn)氫率圖（鹵素離子濃度為0.85M（曲線1~7）、0.93mol/LNH4Cl（曲線9）、0.31mol/LNH4Cl和0.85mol/LNaCl混合溶液（曲線8））[18]Fig.2Curvesofhydrogenyieldrateof1gMgin30mLalkalimetal,alkalineearthmetalhalideandammoniumchloridesolution(halogenionconcentration0.85mol/L(curve1~7),0.93mol/LNH4Cl(curve9),0.31mol/LNH4Cland0.85mol/LNaClmixedsolution(curve8))[18]3添加第二相3.1添加金屬氧化物過渡族金屬氧化物對(duì)Mg水解具有催化的作用。Huang等ADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2017</Year><RecNum>240</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>240</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540888958">240</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Minghong</author><author>Ouyang,Liuzhang</author><author>Chen,Zhiling</author><author>Peng,Chenghong</author><author>Zhu,Xiaoke</author><author>Zhu,Min</author></authors></contributors><titles><title>HydrogenproductionviahydrolysisofMg-oxidecomposites</title><secondary-title>InternationalJournalofHydrogenEnergy</secondary-title></titles><periodical><full-title>InternationalJournalofHydrogenEnergy</full-title></periodical><pages>22305-22311</pages><volume>42</volume><number>35</number><section>22305</section><dates><year>2017</year></dates><isbn>03603199</isbn><urls></urls><electronic-resource-num>10.1016/j.ijhydene.2016.12.099</electronic-resource-num></record></Cite></EndNote>[19]探究了廉價(jià)金屬氧化物Fe2O3、CaO、MoO3、Fe3O4、Nb2O5和TiO2對(duì)Mg水解性能的影響。將Mg和5wt.%金屬氧化物機(jī)械球磨1h后在3.5%NaCl水溶液中水解，發(fā)現(xiàn)除了CaO，其他的金屬氧化物對(duì)Mg的水解均起到了促進(jìn)作用，其中MoO3、Fe2O3和Fe3O4的促進(jìn)作用最為明顯，分別達(dá)到了888mLg-1、869mLg-1、826mLg-1，純鎂的為257mLg-1，而CaO的只有137mLg-1。他們認(rèn)為添加金屬氧化物的水解性能之所以不同是由于他們與Mg原子的粘附力不同所導(dǎo)致的。他們還發(fā)現(xiàn)過渡族金屬Fe的價(jià)態(tài)越高對(duì)Mg的水解性能的提升作用越明顯。無獨(dú)有偶，當(dāng)添加Mo的不同價(jià)態(tài)氧化物及硫化物時(shí)，同樣發(fā)現(xiàn)Mo的價(jià)態(tài)越高對(duì)Mg水解的催化活性越高ADDINEN.CITE<EndNote><Cite><Author>Huang</Author><Year>2017</Year><RecNum>239</RecNum><DisplayText><styleface="superscript">[8,20]</style></DisplayText><record><rec-number>239</rec-number><foreign-keys><keyapp="EN"db-id="tz00tepesapdeye9a9vp9wpkwfes0swpfvp0"timestamp="1540888952">239</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Huang,Minghong</author><author>Ouyang,Liuzhang</author><author>Ye,Jianshan</author><author>Liu,Jiangwen</author><author>Yao,Xiangdong</author><author>Wang,Hui</author><author>Shao,Huaiyu</author><author>Zhu,Min</author></authors></contributors><