本文主要研究内容
作者陆世玉（2019）在《镍（钴）基硫（磷）化物电解水催化剂的纳米调控及其电催化性能研究》一文中研究指出：当前,由于化石燃料的急剧损耗,人类面临着两大世界性问题:1)化石燃料的燃烧造成的环境污染和恶化问题,2)化石燃料的不断损耗,所造成的能源短缺问题。以上两个问题如果不尽快解决,将会大大限制社会和人类的生存和发展。所以寻找和开发清洁、可持续、能量密度高的替代能源已势在必行。在目前发现和开发的多种可持续能源中,氢能源由于具有能量密度高、资源分布广泛、易储存、燃烧产物无污染、可再生等优点,被认为是未来最具有开发潜力的能源之一。电解水技术是一种将电能直接转换为化学能的方法,并可灵活的和其他可再生能源如风能、潮汐能、太阳能等联合使用,同时也可以达到将这些可再生能源以化学能的形式储存起来的目的。这样一来,电解水技术也可以作为一种其他可再生能源的中转体系,可将其他能源转化为氢气或者氧气储存起来。电解水反应可分为阴极的析氢反应和阳极的析氧反应。但是不论阴极和阳极,都需要高效、稳定的电催化剂才能使得水分解反应能够有效的进行。Pt及其合金被认为是析氢反应中催化活性最好的电催化剂,而Ir、Ru及其合金被认为是析氧反应中催化性能最好的电催化剂。但是,遗憾的是Pt、Ir、Ru等这类贵金属存储量较少,并且价格昂贵,抑制了这类电催化剂的大规模生产和实际应用。所以,开发、设计、寻找价格低廉、催化活性高且稳定的非贵金属催化剂已成为目前关注的焦点。本论文主要针对高效、廉价且稳定的电解水催化剂,应用纳米化、孔结构调节、形貌调控、导电载体及表面态调控的技术设计出具有优异催化活性的电催化剂,并进行了相应的机理探讨。论文主要包含四个工作:首先,我们从形貌调控电催化性能的角度出发,利用共沉淀的方法制备了中空多孔磷酸镍纳米球,将其作为高效的析氧催化剂;其次,我们从形貌调控和表面缺陷共同调节电催化性能角度出发,将前一章制备的中空多孔磷酸镍纳米球在还原气氛中高温煅烧,制备富氧缺陷的磷化镍多孔空心球并作为电解水双功能催化剂;随后,我们从掺杂元素调控催化剂表面态的角度出发,利用碳布作为载体,负载双功能催化剂Co0.84Sn0.16P CC;最后,我们同时结合形貌和表面调控,以镍网作为导电载体,负载高效析氢催化剂Ni3Sn2S2@Ni3S2 NF。其具体内容如下:1.从形貌和孔结构改善电催化剂电子传输,提高催化剂电催化能力的角度出发,使用简单的室温沉淀反应制备了无定型的中空多孔磷酸镍纳米球,同时探究了该纳米球的生长过程和生长机制。在测试电化学过程中,研究了不同碳复合中空多孔磷酸镍纳米球催化剂的OER催化性能。最优的催化剂在电流密度为10 mA cm-2的过电势为330 mV,塔菲尔斜率为76.5 mV dec-1。其性能和商业化的RuO2相近,并且在连续OER电解20小时后,未观察到明显的衰减。碳提高了催化剂整体的导电性,多孔和中空的结构提高了磷酸镍在催化过程中的电荷传输能力,并且增加了电解液和催化剂之间的接触面积。2.我们通过控制还原温度,在延续前一章材料的孔结构和形貌的同时,在中空多孔纳米球上引入大量的O空位,制备了富氧空位的中空多孔磷化镍纳米球,同时探究了还原温度对于孔结构的变化及材料形貌的影响。富氧空位的中空多孔磷化镍纳米球的性能远远优于使用NaH2PO2制备的催化剂的性能。最优的HER催化剂在10 mA cm-2的电流密度下的过电位仅为93 mV,并具有优异的电化学稳定性。3.将其它元素掺杂进金属或非金属基来修饰和调节催化剂的物理化学性能和电子结构,可以整体的提高催化剂活性,这也是一种有效且简便的方法。但需要注意的是,这些过渡金属元素本身均具有催化活性,提高的原因可以归功于掺杂元素和催化剂本体的协同作用。不具有催化活性的过渡金属元素掺杂的电催化剂并未被合成,其析氢催化机理也尚不明确。鉴于此,我们将3d过渡金属且不具有催化活性的Sn元素成功掺杂入CoP纳米线中,并调控了Sn元素掺杂进入CoP的含量。实验结果表明,适量的Sn掺杂不仅仅提高了Co1-xSnxP在基底上的分散度,还提高了CoP中Co离子位点的催化活性。最优的Co0.84Sn0.16P CC表现出优异的HER和OER活性。在HER中,当电流密度达到10 mA cm-2时的过电位为60.3 mV,塔菲尔斜率为40.8 mV dec-1。而在OER中,当电流密度达到50 mA cm-2时的过电位为360 mV,对应的塔菲尔斜率为82.8 mV dec-1。4.结合形貌调控和调节催化剂表面态,来影响中间体在电催化剂上的吸附力,从而使得催化剂的性能有所改善。我们制备了分散均匀且密度较高的Ni3Sn2S2量子点锚定在超薄Ni3S2纳米片上（Ni3Sn2S2@Ni3S2）的材料,并将其作为碱性环境下高效的非贵金属氢气析出电催化剂。该纳米催化剂在低电流密度下展现出和贵金属（Pt/C）相似的催化活性,但是在高电流密度下性能将会超越贵金属（Pt/C）。通过对实验结果和理论计算的分析,得出该催化剂性能提高的原因主要归功于可暴露更多催化位点的特殊形貌和原子重组后造成的H-S键的作用削弱。Sn原子的引入,会造成Ni3Sn2S2晶体中未配对的NiA-d轨道的电子离域,使材料的d轨道中心更接近费米能级。于此同时,也会造成Sn-p轨道的电子离域,阻止催化剂表面H-S键的杂化形成,起到优化和调节H原子在电催化剂表面的吸附和脱附作用。
Abstract
dang qian ,you yu hua dan ran liao de ji ju sun hao ,ren lei mian lin zhao liang da shi jie xing wen ti :1)hua dan ran liao de ran shao zao cheng de huan jing wu ran he e hua wen ti ,2)hua dan ran liao de bu duan sun hao ,suo zao cheng de neng yuan duan que wen ti 。yi shang liang ge wen ti ru guo bu jin kuai jie jue ,jiang hui da da xian zhi she hui he ren lei de sheng cun he fa zhan 。suo yi xun zhao he kai fa qing jie 、ke chi xu 、neng liang mi du gao de ti dai neng yuan yi shi zai bi hang 。zai mu qian fa xian he kai fa de duo chong ke chi xu neng yuan zhong ,qing neng yuan you yu ju you neng liang mi du gao 、zi yuan fen bu an fan 、yi chu cun 、ran shao chan wu mo wu ran 、ke zai sheng deng you dian ,bei ren wei shi wei lai zui ju you kai fa qian li de neng yuan zhi yi 。dian jie shui ji shu shi yi chong jiang dian neng zhi jie zhuai huan wei hua xue neng de fang fa ,bing ke ling huo de he ji ta ke zai sheng neng yuan ru feng neng 、chao xi neng 、tai yang neng deng lian ge shi yong ,tong shi ye ke yi da dao jiang zhe xie ke zai sheng neng yuan yi hua xue neng de xing shi chu cun qi lai de mu de 。zhe yang yi lai ,dian jie shui ji shu ye ke yi zuo wei yi chong ji ta ke zai sheng neng yuan de zhong zhuai ti ji ,ke jiang ji ta neng yuan zhuai hua wei qing qi huo zhe yang qi chu cun qi lai 。dian jie shui fan ying ke fen wei yin ji de xi qing fan ying he yang ji de xi yang fan ying 。dan shi bu lun yin ji he yang ji ,dou xu yao gao xiao 、wen ding de dian cui hua ji cai neng shi de shui fen jie fan ying neng gou you xiao de jin hang 。Ptji ji ge jin bei ren wei shi xi qing fan ying zhong cui hua huo xing zui hao de dian cui hua ji ,er Ir、Ruji ji ge jin bei ren wei shi xi yang fan ying zhong cui hua xing neng zui hao de dian cui hua ji 。dan shi ,wei han de shi Pt、Ir、Rudeng zhe lei gui jin shu cun chu liang jiao shao ,bing ju jia ge ang gui ,yi zhi le zhe lei dian cui hua ji de da gui mo sheng chan he shi ji ying yong 。suo yi ,kai fa 、she ji 、xun zhao jia ge di lian 、cui hua huo xing gao ju wen ding de fei gui jin shu cui hua ji yi cheng wei mu qian guan zhu de jiao dian 。ben lun wen zhu yao zhen dui gao xiao 、lian jia ju wen ding de dian jie shui cui hua ji ,ying yong na mi hua 、kong jie gou diao jie 、xing mao diao kong 、dao dian zai ti ji biao mian tai diao kong de ji shu she ji chu ju you you yi cui hua huo xing de dian cui hua ji ,bing jin hang le xiang ying de ji li tan tao 。lun wen zhu yao bao han si ge gong zuo :shou xian ,wo men cong xing mao diao kong dian cui hua xing neng de jiao du chu fa ,li yong gong chen dian de fang fa zhi bei le zhong kong duo kong lin suan nie na mi qiu ,jiang ji zuo wei gao xiao de xi yang cui hua ji ;ji ci ,wo men cong xing mao diao kong he biao mian que xian gong tong diao jie dian cui hua xing neng jiao du chu fa ,jiang qian yi zhang zhi bei de zhong kong duo kong lin suan nie na mi qiu zai hai yuan qi fen zhong gao wen duan shao ,zhi bei fu yang que xian de lin hua nie duo kong kong xin qiu bing zuo wei dian jie shui shuang gong neng cui hua ji ;sui hou ,wo men cong can za yuan su diao kong cui hua ji biao mian tai de jiao du chu fa ,li yong tan bu zuo wei zai ti ,fu zai shuang gong neng cui hua ji Co0.84Sn0.16P CC;zui hou ,wo men tong shi jie ge xing mao he biao mian diao kong ,yi nie wang zuo wei dao dian zai ti ,fu zai gao xiao xi qing cui hua ji Ni3Sn2S2@Ni3S2 NF。ji ju ti nei rong ru xia :1.cong xing mao he kong jie gou gai shan dian cui hua ji dian zi chuan shu ,di gao cui hua ji dian cui hua neng li de jiao du chu fa ,shi yong jian chan de shi wen chen dian fan ying zhi bei le mo ding xing de zhong kong duo kong lin suan nie na mi qiu ,tong shi tan jiu le gai na mi qiu de sheng chang guo cheng he sheng chang ji zhi 。zai ce shi dian hua xue guo cheng zhong ,yan jiu le bu tong tan fu ge zhong kong duo kong lin suan nie na mi qiu cui hua ji de OERcui hua xing neng 。zui you de cui hua ji zai dian liu mi du wei 10 mA cm-2de guo dian shi wei 330 mV,da fei er xie lv wei 76.5 mV dec-1。ji xing neng he shang ye hua de RuO2xiang jin ,bing ju zai lian xu OERdian jie 20xiao shi hou ,wei guan cha dao ming xian de cui jian 。tan di gao le cui hua ji zheng ti de dao dian xing ,duo kong he zhong kong de jie gou di gao le lin suan nie zai cui hua guo cheng zhong de dian he chuan shu neng li ,bing ju zeng jia le dian jie ye he cui hua ji zhi jian de jie chu mian ji 。2.wo men tong guo kong zhi hai yuan wen du ,zai yan xu qian yi zhang cai liao de kong jie gou he xing mao de tong shi ,zai zhong kong duo kong na mi qiu shang yin ru da liang de Okong wei ,zhi bei le fu yang kong wei de zhong kong duo kong lin hua nie na mi qiu ,tong shi tan jiu le hai yuan wen du dui yu kong jie gou de bian hua ji cai liao xing mao de ying xiang 。fu yang kong wei de zhong kong duo kong lin hua nie na mi qiu de xing neng yuan yuan you yu shi yong NaH2PO2zhi bei de cui hua ji de xing neng 。zui you de HERcui hua ji zai 10 mA cm-2de dian liu mi du xia de guo dian wei jin wei 93 mV,bing ju you you yi de dian hua xue wen ding xing 。3.jiang ji ta yuan su can za jin jin shu huo fei jin shu ji lai xiu shi he diao jie cui hua ji de wu li hua xue xing neng he dian zi jie gou ,ke yi zheng ti de di gao cui hua ji huo xing ,zhe ye shi yi chong you xiao ju jian bian de fang fa 。dan xu yao zhu yi de shi ,zhe xie guo du jin shu yuan su ben shen jun ju you cui hua huo xing ,di gao de yuan yin ke yi gui gong yu can za yuan su he cui hua ji ben ti de xie tong zuo yong 。bu ju you cui hua huo xing de guo du jin shu yuan su can za de dian cui hua ji bing wei bei ge cheng ,ji xi qing cui hua ji li ye shang bu ming que 。jian yu ci ,wo men jiang 3dguo du jin shu ju bu ju you cui hua huo xing de Snyuan su cheng gong can za ru CoPna mi xian zhong ,bing diao kong le Snyuan su can za jin ru CoPde han liang 。shi yan jie guo biao ming ,kuo liang de Sncan za bu jin jin di gao le Co1-xSnxPzai ji de shang de fen san du ,hai di gao le CoPzhong Coli zi wei dian de cui hua huo xing 。zui you de Co0.84Sn0.16P CCbiao xian chu you yi de HERhe OERhuo xing 。zai HERzhong ,dang dian liu mi du da dao 10 mA cm-2shi de guo dian wei wei 60.3 mV,da fei er xie lv wei 40.8 mV dec-1。er zai OERzhong ,dang dian liu mi du da dao 50 mA cm-2shi de guo dian wei wei 360 mV,dui ying de da fei er xie lv wei 82.8 mV dec-1。4.jie ge xing mao diao kong he diao jie cui hua ji biao mian tai ,lai ying xiang zhong jian ti zai dian cui hua ji shang de xi fu li ,cong er shi de cui hua ji de xing neng you suo gai shan 。wo men zhi bei le fen san jun yun ju mi du jiao gao de Ni3Sn2S2liang zi dian mao ding zai chao bao Ni3S2na mi pian shang （Ni3Sn2S2@Ni3S2）de cai liao ,bing jiang ji zuo wei jian xing huan jing xia gao xiao de fei gui jin shu qing qi xi chu dian cui hua ji 。gai na mi cui hua ji zai di dian liu mi du xia zhan xian chu he gui jin shu （Pt/C）xiang shi de cui hua huo xing ,dan shi zai gao dian liu mi du xia xing neng jiang hui chao yue gui jin shu （Pt/C）。tong guo dui shi yan jie guo he li lun ji suan de fen xi ,de chu gai cui hua ji xing neng di gao de yuan yin zhu yao gui gong yu ke bao lou geng duo cui hua wei dian de te shu xing mao he yuan zi chong zu hou zao cheng de H-Sjian de zuo yong xiao ruo 。Snyuan zi de yin ru ,hui zao cheng Ni3Sn2S2jing ti zhong wei pei dui de NiA-dgui dao de dian zi li yu ,shi cai liao de dgui dao zhong xin geng jie jin fei mi neng ji 。yu ci tong shi ,ye hui zao cheng Sn-pgui dao de dian zi li yu ,zu zhi cui hua ji biao mian H-Sjian de za hua xing cheng ,qi dao you hua he diao jie Hyuan zi zai dian cui hua ji biao mian de xi fu he tuo fu zuo yong 。
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论文作者分别是来自西南大学的陆世玉，发表于刊物西南大学2019-09-24论文，是一篇关于碱性电解水论文,氢析出反应论文,氧析出反应论文,磷化物论文,硫化物论文,磷酸盐论文,西南大学2019-09-24论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自西南大学2019-09-24论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：碱性电解水论文; 氢析出反应论文; 氧析出反应论文; 磷化物论文; 硫化物论文; 磷酸盐论文; 西南大学2019-09-24论文;