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金属有机框架材料åQ?/span>MOFåQ‰å…·æœ‰é«˜çš„æ¯”表面¿U¯å’Œå¯ä¿®é¥°çš„表面åQŒä‹É之成ä¸ÞZº†æ–°èƒ½æºææ–™é¢†åŸŸçš„研究热点之一。近òq´æ¥åQ?/span>MOFå?qi¨¢ng)其衍生物的合成和应用得åˆîCº†çˆ†ç‚¸å¼?/span>发展åQŒè¢«òq¿æ³›åº”用于电(sh¨´)池,催化åQŒæ°”体分¼›È­‰è¯¸å¤šé¢†åŸŸåQŒç‰¹åˆ«æ˜¯åŸÞZºŽMOF制备功能多孔¼„³ç¬¼ææ–™å‡­å€Ÿå…¶ä¼—å¤šä¼˜åŠ¿è€Œè¶Šæ¥è¶ŠæˆäØ“(f¨´)研究热点。然而,传统MOF制备¼„³ç¬¼å¤§å¤šæ•?/span>采用湿化学方法,合成手段单一åQŒäñ”量较?y¨­u)®ï¼Œæ‰€ä½¿ç”¨çš„æœ‰æœºæº¶å‰‚对环境æœ?/span>危害åQŒå› æ­¤å¼€å‘新型绿色高效合成功èƒ?/span>工艺势在必行ã€?/span>本研½I¶ä»¥MOF材料为基¼‹€åQŒå¼€å‘出了一¿Uä¸åŒäºŽä¼ ç»Ÿæ¹¿åŒ–学方æ³?/span>åQ?/span>åÏx°”è’?/span>MOF½{–略合成了具有开攑֞‹å­”道çš?/span>多孔¼„³ç¬¼ææ–™åQ?/span>其表现出高效é”?/span>åŸ?/span>èƒ?/span>é‡?/span>储存能力和超高的化学½E›_®šæ€?/span>åQ?/span>䏸™¿›ä¸€æ­¥åˆæˆå’Œåˆ©ç”¨åŠŸèƒ½åŒ–å¤šå­”ææ–™æä¾›äº†æ–ÒŽ(gu¨©)³•学和实验基础åQ?/span>实现了对MOF衍生物结构、åŞ貌和性能çš?/span>¾_„¡¡®æŽ§åˆ¶åQ?/span>大大拓展äº?/span>MOF材料在能源领域的应用ã€?/span>



日本ChEM-OIL/南科大徐强教æŽ?/span>è¯ùN¢˜¾l?/span>在其先前研究的基¼‹€ä¸?/span>åQ?/span>Adv. Mater. 2016, 28, 6391; Angew. Chem. Int. Ed. 2020, 59, 7384; Adv. Mater. 2019, 31, 1904689; Angew. Chem. Int. Ed. 2020, 59, 21360; Energy Environ. Sci., 2017, 10, 1770; Nat. Rev. Mater. 2018, 3, 17075.åQ‰ï¼Œ½Hç ´æ€?/span>发展了一¿Uç®€å•有效的固态气è’?/span>MOFå?/span>成策略制备了壁端开口的功能¼„³ç¬¼ææ–™ã€‚启发于我们日常蒔R¦’头过½E‹ï¼Œç ”ç©¶äº?/span>员通过利用½Ž€å•固态次¼‚·é…¸é’ ç‰©è´¨åœ¨å—热条äšg下易分解产生¼‚·åŒ–氢气氛基¼‹€ä¸?/span>åQ?/span>巧妙的引å…?/span>MOFåQŒåœ¨ž®é—­æ¡äšg下对MOF˜q›è¡Œâ€?/span>è’?/span>â€?/span>的过½E‹ã€?/span>所产生的磷化氢气体å¯?/span>MOF˜q›è¡Œå¯æŽ§è…èš€åQŒå†¾lè¿‡˜q›ä¸€æ­¥é«˜æ¸©ç¢³åŒ–后得到具备壁上开å?/span>均匀æ°?/span>/¼‚ähŽºæ‚çš„å¤šå­”¼„³ç¬¼ææ–™ã€‚开攑֞‹çš„孔道设计可以大大提å?/span>¼„³ç¬¼ææ–™åœ¨ç¦»å­å­˜å‚¨ä¼ è¾“过½E‹ä¸­çš„传质效率,而在¼„Ïxæ–™ä¸­åŸºå…ƒåŒ–位ç‚ÒŽ(gu¨©)Û/¼‚·å…ƒç´ çš„æŽºæ‚åˆ?/span>有利于优化锌¼›Õd­çš„化学吸附,降低‹zÕdŒ–壁垒åQŒæå‡åŠ¨åŠ›å­¦æ•ˆç”¨ã€?/span>如此双管齐下åQ?/span>凭借以上优势该æ–ÒŽ(gu¨©)³•所制备的碳½W¼ææ–?/span>应用äº?/span>æ°´ç³»é”Œç¦»å­æØœåˆè¶…¾U§ç”µ(sh¨´)容器åQ?/span>ZHSCåQ?/span>ä½œäØ“(f¨´)¼„Ïx­£æžï¼Œè¡¨çްå‡?/span>宽电(sh¨´)压运行范å›ß_(d¨¢)¼Œ­‘…高的比定w‡/能量密度和长旉™—´å¾ªçŽ¯å¯¿å‘½åQ?/span>˜q?/span>一æ­?/span>应用åˆ?/span>软包器äšg中,也表现出不错的宽温度范围应用效果åQŒæ»¡­‘³äh们生产生‹zÕdŸºæœ¬æ¸©åº¦éœ€æ±?/span>ã€?/span>


å›?/span>1. â€?span style="line-height:28px;font-family:å¾®èÊY雅黑;">è’?/span>”MOF制备壁上开口碳½W¼æ“ä½œæµ½E‹ç¤ºæ„å›¾


¼„³ç¬¼ææ–™çš„可控制å¤?/strong>


ž®?/span>MOF材料å’?/span>‹Æ¡ç£·é…”R’ å‡åŒ€æ··åˆå¤„理后封闭放入配备有真空-å……æ°”¾pȝ»Ÿçš„管式炉ä¸?/span>åQ?/span>先升温到300oCåQ?/span>在此温度下保持两个小时后åQŒè¿›ä¸€æ­¥å‡åˆ°é«˜æ¸©å®Œæˆç¢³åŒ?/span>ã€?/span>300oCæ—Óž¼ŒMOF材料保持良好åQŒæ­¤æ—¶æ¬¡¼‚·é…¸é’ ä¼š(x¨¬)逐步分解产生¼‚·åŒ–氢气体,在该ž®é—­æ¡äšg下对MOF晉™¢å‘生选择性腐蚀。该æ–ÒŽ(gu¨©)³•不需要ä‹É用ä“Q何有机溶剂,直接在固态条件下â€?span style="font-family:å¾®èÊY雅黑;">熏蒸â€?/span>MOFåQ?/span>最¾lˆå¾—åˆ?/span>äº?/span>å£?/span>ç«?/span>开口的多孔¼„³ç¬¼ææ–™ã€‚实验表明该æ–ÒŽ(gu¨©)³•½Ž€å•有效,是一¿Uæ™®é€‚æ–¹æ³?/span>åQ?/span>既能实现å¯ÒŽ(gu¨©)æ–™åŞ貌的¾_„¡¡®æŽ§åˆ¶åQ?/span>又能构徏N/P掺杂的高效活性位点,利于化学吔R™„锌离子,在宏观和微观两个层面上实çŽîCº†ææ–™çš„定向设计(å›?/span>1所½C?/span>åQ?/span>ã€?/span>


å›?/span>2. 所制备¼„?/span>½W¼ææ–™è¡¨å¾?/span>


¼„³ç¬¼ææ–™çš„表征与储能应用


所合成¼„³ç¬¼ç”?/span>SEMåQ?/span>TEMåQ?/span>XRD½{‰åšäº†è¡¨å¾?/span>åQ?/span>文章有介¾l?/span>åQ?/span>不多赘述ã€?/span>物理表征证实了该­‘…结构碳½W¼ææ–™çš„æˆåŠŸåˆæˆåQˆå›¾2所½Cºï¼‰(j¨ª)。作为对比,直接¼„›_Œ–MOFä¼?x¨¬)生成表面完整的¼?/span>材料åQŒæ¯”表面¿U¯å°åQŒä¸åˆ©äºŽåº•物的有效传输ã€?/span>利用气蒸MOF法制备的¼„³ç¬¼ææ–™å‘ˆçŽ°å‡ä¸€çš„å£ç«¯å¼€å£åŞ貌,在大大提升了¼„Ïxæ–™çš„æ¯”表面积的同æ—Óž¼Œå®žçŽ°äº†å¤šå…ƒå­”å¾„çš„åˆ†å¸ƒåQŒä‹É得材料在传质发面效果显著ã€?/span>EDS mapping证实åQŒå¾®è§‚上åQŒè¯¥¾l“构表面均匀的分布着异原å­?/span>N/P掺杂的活性位ç‚?/span>, 该活性位点可以更加有效的寚w”Œ¼›Õd­˜q›è¡ŒåŒ–学吔R™„åQŒé™ä½Žæ´»åŒ–能åž?/span>åQ?/span>使得è¯?/span>¼„³ç¬¼ææ–™æ˜„¡Ž°å‡ÞZ¼˜å¼‚的锌基ç”?sh¨´)存储性能ã€?br />

ž®†æ‰€åˆæˆçš„碳½W¼ææ–™ä½œä¸ºç¢³æ­£æžææ–™åº”用于锌¼›Õd­æ··åˆåž‹è¶…¾U§ç”µ(sh¨´)容器åQ?/span>ZHSCåQ?/span>。相对于其他同等条äšg下制备的¼„?/span>材料åQ?/span>实验表明åQŒè¿™¿Uå£ç«¯å¼€å£çš„N/P掺杂的碳½W¼ææ–™è¡¨çŽ°å‡º­‘…高的锌基电(sh¨´)化学储能性能和长旉™—´å¾ªçޝ½E›_®šæ€§ï¼ˆ30万次循环保持96.5%åQ?/span>åQŒåƈåŸÞZºŽæ­¤ç»„装成软包器äšgå?/span>åQŒè¡¨çŽ°å‡ºä¼˜å¼‚çš?/span>å…?/span>攄¡”µ(sh¨´)性能å’?/span>宽温度范围实用效æž?/span>ã€?/span>


¾l“论与展æœ?/strong>


本工作首‹Æ?/span>开发了一¿Uå›ºæ€æ°”“蒸”MOF制备¼„³ç¬¼ææ–™çš„æœ‰æ•ˆæ–¹æ³?/span>åQ?/span>开辟了一条可控合成功èƒ?/span>多孔材料的新途径ã€?/span>˜q™é¡¹æˆæžœä¸ä»…提供了一¿Uå…¨æ–°çš„½{–略合成壁上开口的¼„³ç¬¼ææ–™, æ›?/span>ä¸ÞZ¼˜åŒ–设è®?/span>MOF衍生材料åœ?/span>ç”?sh¨´)化学能源领域的应用打下了基¼‹€ã€?/span>

Chun-Chao Hou, et al, A Gas-Steamed MOF Route to P-Doped Open Carbon Cages with Enhanced Zn-Ion Energy Storage Capability and Ultrastability, Angew. Chem. Int. Ed. 2021, 2101698


作者简�/strong>


½W¬ä¸€ä½œè€?/span>-侯春æœ?/span>博士åQ?/span>

侯春朝博士,äº?/span>2017中科院理化技术研½I¶æ‰€èŽ·å¾—åšå£«å­¦ä½åQŒéšåŽèʎ日本加入徐强教授è¯ùN¢˜¾l„å­¦ä¹?f¨¤n)。已在JACSåQ?/span>Angew½{‰æ‚志发表文ç«?/span>å¤?/span>½‹‡ï¼Œç›®å‰ä¸»è¦ä»Žäº‹åŸÞZºŽ¾U³ç±³ææ–™çš„可控合æˆ?/span>åQŒå•原子/团簇催化å?qi¨¢ng)其在ç”?sh¨´)化学应用½{?/span>æ–šw¢ç ”ç©¶ã€?/span>

通讯作è€?/span>-徐强教授åQ?/span>

徐强教授åQŒå—方科技大学讲席教授åQŒï¼ˆå‰ï¼‰(j¨ª)日本产业技术综合研½I¶æ‰€(AIST)-京都大学化学能源材料创新实验室(ChEM-OILåQ‰ä¸»ä»?/span>åQ?/span>日本工程院、欧‹z²ç§‘学院、印度国家科学院院士。主要研½I‰™¢†åŸŸæ˜¯¾U³ç±³¾l“构材料的化学与应用åQˆå°¤å…¶æ˜¯å‚¬åŒ–和能源等斚w¢åQ‰ã€‚迄今发表论æ–?/span>400余篇åQŒè®ºæ–‡è¢«å¼•大äº?/span>40000‹Æ¡ï¼Œh-index >105 (Web of ScienceåQ‰ã€‚于2012òq´èŽ·å¾—æ±¤‹‚®èµ\透研½I¶å‰æ²¿å¥–åQ?/span>Thomson Reuters Research Front AwardåQ‰ï¼Œ2019òq´èŽ·‹zªå ¡å¥–,è¢?/span>Thomson Reuters / Clarivate Analyticsè¯„äØ“(f¨´)高被引科学家åQ?/span>2014-2020òqß_(d¨¢)¼‰(j¨ª)。担ä»Õd¤šå®¶æœŸåˆŠçš„¾~–辑/¾~–å§”å?qi¨¢ng)顾问委员,包括åQ?/span>EnergyChemåQ?/span>ElsevieråQŒä¸»¾~–)(j¨ª)åQ?/span>Coordination Chemistry ReviewsåQ?/span>ElsevieråQŒå‰¯ä¸È¼–åQ‰ï¼ŒChemåQ?/span>Cell PressåQ‰ï¼ŒMatteråQ?/span>Cell PressåQ‰ï¼ŒChemistry-an Asian JournalåQ?/span>WileyåQ?/span>, Small Structures (Wiley) ½{‰ã€?/span>


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https://onlinelibrary.wiley.com/doi/10.1002/adma.202101698

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