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异样的太阳能电池：捕获光和CO2,产生可燃燃料（附专利25件）
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异样的太阳能电池：捕获光和CO2,产生可燃燃料（附专利25件）
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据伊利诺伊大学芝加哥分校（University of Illinois at Chicago，UIC）2016年7月28日提供的消息, 该大学的研究人员设计了一种异样的太阳能电池,可以廉价而且有效地将大气中的CO2直接转化为可用的碳氢化合物燃料,并只使用太阳光作为能源。这一研究成果2016年7月29日已经在《科学》（Science）杂志网站发表——Mohammad Asadi, Kibum Kim, Cong Liu, Aditya Venkata Addepalli, Pedram Abbasi, Poya Yasaei, Patrick Phillips, Amirhossein Behranginia, José M. Cerrato, Richard Haasch, Peter Zapol, Bijandra Kumar, Robert F. Klie, Jeremiah Abiade, Larry A. Curtiss（Email: curtiss@anl.gov）, Amin Salehi-Khojin（Email: salehikh@uic.edu）. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science，2016, 353(6298): 467-470. DOI: 10.1126/science.aaf4767. 此研究项目是由美国国家科学基金会和美国能源部资助的，并且已经向专利机构提交了专利申请(Catalysts for Carbon Dioxide Conversion, United States Patent Application 20160145752, Download PDF 20160145752, Download PDF WO/2014/210484A1)。
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Simulated sunlight powers a solar cell that converts atmospheric carbon dioxide directly into syngas. Credit: University of Illinois at Chicago/Jenny Fontaine |
UIC的此项研究成果涉及到的太阳能电池，不同于传统的 太阳能电池，传统的太阳能电池是将太阳能转换为电能,再将电能存储在沉重的电池中,而新装置本质上像是一种植物工厂，是将大气中的CO2转化为燃料,同时解决污染与能源两个关键性问题。像这样的“人工叶片”的太阳能农场，可以从大气中清除大量的CO2并有效地产生高能量燃料。
UIC的机械与工业工程助理教授，也是该研究的主要作者Amin Salehi-Khojin说：“新太阳能电池不是光伏电池，而是光合成系统。不是以化石燃料（fossil fuels）燃烧放出温室气体的不可持续的单向路线而获得能量,我们现在可以使此过程逆转，利用太阳光回收大气碳（CO2）使其转化为燃料。”但是，植物生产燃料是以糖的形式存在，而人工叶片提供的合成气（syngas or synthesis gas）是氢气(H2)和CO的混合物，合成气可直接燃烧,或转化为柴油或其他碳氢化合物燃料。（While plants produce fuel in the form of sugar, the artificial leaf delivers syngas, or synthesis gas, a mixture of hydrogen gas and carbon monoxide. Syngas can be burned directly, or converted into diesel or other hydrocarbon fuels.）。但实际上原文中的反应是选择性地将CO2还原成CO，通过太阳能电池产生的电子和正电空穴，在电池的二硒化钨阴极上发生质子参与的还原反应产生水和一氧化碳，同时在电池的钴氧化物阳极上发生水的氧化反应产生O2和质子。氢气是需要被选择性抑制的副产物，它来自于质子在阴极上不经CO2参与而被直接还原的副反应。离子液作为介质帮助提高了反应的效率。将CO2转化为燃料的能力，在成本上相当于老式的化石燃料转化为一加仑汽油的成本。
将CO2转化为可燃式碳的化学反应被称为还原反应,它是氧化反应的逆反应，燃烧就是氧化反应。工程师们一直在探索采用不同催化剂来驱动CO2还原,但到目前为止,这类反应的效率很低,而且催化剂依靠昂贵的银等贵金属。Amin Salehi-Khojin说：“我们需要的是一个具有非凡性质的化学物质新家族。”
Amin Salehi-Khojin和他的同事关注具有纳米结构的过渡金属二硫属化物（transition metal dichalcogenides简称TMDCs），可以用MX2来表示，M代表过渡金属，而X代表硫族元素如S、Se或Te。用此类化合物来作为催化剂,将它们与一种非传统的离子液体电解质配对在2个隔间内构成电解质,组成3电极电化学电池。他们发现最好的几种催化剂是二硒化钨纳米薄片（nanoflake tungsten diselenide）。
20世纪60年代以来已经制备出数十种二硫属过渡金属化合物，有人将其分为金属类、半导体类、绝缘体类以及超导体类：
CO2被还原的示意图
下面照片是UIC机械与工业工程助理教授Amin Salehi-Khojin（左）和博士后研究者穆罕默德·阿沙迪（MohammadAsadi）以及他们的将大气中CO2直接转化为合成气的突破性太阳能电池。
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Amin Salehi-Khojin, UIC assistant professor of mechanical and industrial engineering (left), and postdoctoral researcher Mohammad Asadi with their breakthrough solar cell that converts atmospheric carbon dioxide directly into syngas. Credit: University of Illinois at Chicago/Jenny Fontaine |
上述论文的第一作者，UIC的博士后研究者穆罕默德·阿沙迪说：“新催化剂更加活跃,更容易打开CO2中的C-O之间的化学键。”事实上,新催化剂催化能力不仅要比贵金属催化剂快1000倍，而且其成本仅仅是贵金属催化剂的1/20。其他研究人员利用TMDC催化剂通过其他方式来制氢,但没有利用其来还有CO2,因为此催化剂无法是其反应发生。
Amin Salehi-Khojin指出：“此催化剂之所以难以催化此反应，是因为催化剂的活性位点中毒和氧化。”而他们的最新研究结果有所突破,是使用了被称为乙基-甲基咪唑四氟硼酸盐（ethyl-methyl-imidazolium tetrafluoroborate）的离子液体,与水按照各占一半的比例混合。Amin Salehi-Khojin说：“水和离子液体的组合起到了一种助催化剂（co-catalyst）的作用,在严酷的还原反应条件下保护了催化剂的活性位点。”
UIC的人工树叶由负责采光的18 cm2的两个三结光伏电池构成，阴极一侧是二硒化钨和离子液体助催化系统，而阳极是浸在磷酸钾电解质中的氧化钴。当100 W/m2光使电池充电时，在阴极就有CO和H2气泡逸出，同时在阳极则产生自由氧和氢离子。100 W/m2的能量密度应为有效的太阳能利用密度，太阳能地表平均密度约1000 W/m2。穆罕默德·阿沙迪说：“氢离子通过隔膜扩散到阴极,参与CO2的还原反应。”
Amin Salehi-Khojin说这项技术不仅应该适应大规模使用,如太阳能农场等,而且也适宜于小规模应用。如果火星上确实有水存在，这种人工树叶在未来有可能在火星上派上用场，因为火星上那层薄薄的大气主要是由遗留下的CO2（95.3%）加上N2（2.7%）、氩气（1.6%）和微量的氧气（0.15%）和水汽（0.03%）组成的。2015年3月6日，科学家称火星表面曾非常湿润，含水量超过北冰洋(科学家：火星表面曾非常湿润含水量超过北冰洋．凤凰网,引用日期2015-03-09)。2015年9月29日，美国宇航局称最新证据表明此前在火星表面一些陨坑坑壁上观察到的神秘暗色条纹可能与间歇性出现的液态水体有关。来自卫星的数据表明这些出现在坑壁上的暗色条纹可能是含盐水体沉积过程产生的结果。尤为关键的一点在于，这种含盐水体将能够改变火星表面水体的冰点与沸点，从而使得液态水体在火星地表的存在成为可能(美国宇航局确认火星地表存在液态水.新浪科技,2015-09-29)。不过这些结果还需要得到进一步证实。
美国科学基金会（NSF）项目主任罗伯特·麦凯布(Robert McCabe)说:UIC的“这项工作适宜于NSF支持的具有重大历史意义的基础研究，可以直接转化为有价值的技术和工程的成就。其结果很好地将实验和计算研究融为一体，获得了具有独特电子性质的过渡金属二硫属化物（transition metal dichalcogenides）。研究小组将机械洞察力与某些聪明的电化学工程结合在一起，在能量转换和环境有关的催化大挑战领域取得了重大进展。”
更多信息请浏览原文或者Ionic liquid catalyst helps turn emissions into fuel；
Sunlight turns carbon dioxide to methane
Small and salty CO2 reduction scheme
Most artificial photosynthesis approaches focus on making hydrogen. Modifying CO2, as plants and microbes do, is more chemically complex. Asadi et al. report that fashioning WSe2 and related electrochemical catalysts into nanometer-scale flakes greatly improves their activity for the reduction of CO2 to CO. An ionic liquid reaction medium further enhances efficiency. An artificial leaf with WSe2 reduced CO2 on one side while a cobalt catalyst oxidized water on the other side.
Abstract
Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes in efficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion toc arbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter,CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 persecond at a low overpotential of 54 millivolts. We also applied this catalystin a light-harvesting artificial leaf platform that concurrently oxidized waterin the absence of any external potential.
与TMDC催化剂有关的专利文献
| Match | Document | Document Title | Score |
|---|---|---|---|
| 1 | 5279720 | Electrophoretic deposition of transition metal dichalcogenides This invention relates to a method of depositing thin coatings of transition metal dichalcogenides on substrates having an electrically-conductive surface. The transition metal dichalcogenide... | 999 |
| 2 | EP0242804A2 | Novel transition metal dichalcogenide catalysts. A novel flocculated methanation, hydrogenation or hydrodesulfurization catalyst of the form MS2:Y:Z wherein MS2 is a single layer transition metal dichalcogenide sulfide, Y is a promoter substance... | 986 |
| 3 | US20160181516 | PHASE TRANSFORMATION IN TRANSITION METAL DICHALCOGENIDES Devices including transition metal dichalcognides and methods of forming and operating such devices are disclosed. In one disclosed method, a layer of a transition metal dichalcogenide is... | 984 |
| 4 | EP0242804A3 | NOVEL TRANSITION METAL DICHALCOGENIDE CATALYSTS Abstract of EP0242804 A novel flocculated methanation, hydrogenation or hydrodesulfurization catalyst of the form MS2:Y:Z wherein MS2 is a single layer transition metal dichalcogenide sulfide, Y... | 982 |
| 5 | 4853359 | Novel transition metal dichalcogenide catalysts A novel flocculated methanation, hydrogenation or hydrodesulfurization catalyst of the form MS2 :Y:Z wherein MS2 is a single layer transition metal dichalcogenide sulfide, Y is a promoter... | 981 |
| 6 | US20150118467 | TRANSITION METAL DICHALCOGENIDE AEROGELS AND METHODS OF PREPARATION AND USE Methods of forming transition metal dichalcogenide aerogels are provided. Some methods include adding at least one solvent to one or more two-dimensional transition metal dichalcogenide sheets to... | 973 |
| 7 | WO/1993/011283A1 | ELECTROPHORETIC DEPOSITION OF TRANSITION METAL DICHALCOGENIDES This invention relates to a method of depositing thin coatings of transition metal dichalcogenides on substrates having an electrically-conductive surface. The transition metal dichalcogenide... | 961 |
| 8 | 4383088 | Organic polymer layered dichalcogenides Organic polymer layered dichalcogenides, such as a transition metal metallocene dichalcogenide-substituted styrene divinylbenzene copolymer, are useful as the cathode active material for lithium... | 900 |
| 9 | WO/1999/052815A1 | SOLUBLE METAL HYDRIDE/TRANSITION METAL DICHALCOGENIDE ALLOYS A new class of metal hydride alloy and processes for forming these alloys is disclosed. The alloys are comprised essentially of organically soluble metal hydrides and single molecular layer type... | 886 |
| 10 | 6143359 | Soluble metal hydride/transition metal dichalcogenide alloys A new class of metal hydride alloy and processes for forming these alloys is disclosed. The alloys are comprised essentially of organically soluble metal hydrides and single molecular layer type... | 885 |
| 11 | 4822590 | Forms of transition metal dichalcogenides Novel single layer materials of the form MX2, where MX2 is a layer-type dichalcogenide such as MoS2, TaS2, WS2, or the like, exfoliated by intercalation of an alkali metal, and immersion in water,... | 797 |
| 12 | US20040062708 | Process for the synthesis of nanotubes of transition metal dichalcogenides A process of the synthesis of nanotubes of transition metal dichalcogenides by chemical transport with the addition of fullerences is provided to obtain nanotubes of transistion metal... | 763 |
| 13 | WO/2015/091781A2 | METHOD OF PRODUCING TRANSITION METAL DICHALCOGENIDE LAYER Method of producing one or more transition metal dichalcogenide (MX2) layers on a substrate, comprising the steps of: obtaining a substrate having a surface and depositing MX2 on the surface using... | 745 |
| 14 | US20100129285 | Process for the Synthesis of Nanotubes and Fullerene-Like Nanostructures of Transition Metal Dichalcogenides, Quasi One-Dimensional Structures of Transition Metals and Oxides of Transition Metals The object of the invention is a process for the synthesis of nanotubes of transition metal dichalcogenides, of fullerene-like nanostructures of transition metal dichalcogenides, of nanotubes of... | 741 |
| 15 | 5279805 | Gas storage using transition metal dichalcogenides Hydrogen and gaseous hydrocarbons are stored by introducing the gases into a transition metal dichalcogenide having the formula MX2. M is selected from the group consisting of Mo, W and Ti and X... | 730 |
| 16 | 8007756 | Process for the synthesis of nanotubes and fullerene-like nanostructures of transition metal dichalcogenides, quasi one-dimensional structures of transition metals and oxides of transition metals The object of the invention is a process for the synthesis of nanotubes of transition metal dichalcogenides, of fullerene-like nanostructures of transition metal dichalcogenides, of nanotubes of... | 728 |
| 17 | WO/1993/022236A1 | GAS STORAGE USING TRANSITION METAL DICHALCOGENIDES Hydrogen and gaseous hydrocarbons are stored by introducing the gases into a transition metal dichalcogenide having the formula MX2. M is selected from the group consisting of Mo, W and Ti and X... | 694 |
| 18 | WO/2002/030814A1 | A PROCESS FOR THE SYNTHESIS OF NANOTUBES OF TRANSITION METAL DICHALCOGENIDES The invention relates to a process for the synthesis of nanotubes of transition metal dichalcogenides by the method of chemical transport with the addition of fullereness. According to this... | 666 |
| 19 | WO/2008/121081A3 | A PROCESS FOR THE SYNTHESIS OF NANOTUBES AND FULLERENE-LIKE NANOSTRUCTURES OF TRANSITION METALS DICHALCOGENIDES, QUASI ONE-DIMENSIONAL STRUCTURES OF TRANSITION METALS AND OXIDES OF TRANSITION METALS The object of the invention is a process for the synthesis of nanotubes of transition metal dichalcogenides, of fullerene-like nanostructures of transition metal dichalcogenides, of nanotubes of... | 636 |
| 20 | WO/2008/121081A2 | A PROCESS FOR THE SYNTHESIS OF NANOTUBES AND FULLERENE-LIKE NANOSTRUCTURES OF TRANSITION METALS DICHALCOGENIDES, QUASI ONE-DIMENSIONAL STRUCTURES OF TRANSITION METALS AND OXIDES OF TRANSITION METALS The object of the invention is a process for the synthesis of nanotubes of transition metal dichalcogenides, of fullerene-like nanostructures of transition metal dichalcogenides, of nanotubes of... | 633 |
| 21 | US20020164521 | Novel applications of exfoliated transition metal dichalcogenides to electrochemical fuel cells Application of two-dimensional materials (TDMs) that are exfoliated transition metal dichalcogenides in electrochemical fuel cells to remove contaminants that are harmful to the fuel cells; to... | 619 |
| 22 | EP2132142B1 | A PROCESS FOR THE SYNTHESIS OF NANOTUBES AND FULLERENE-LIKE NANOSTRUCTURES OF TRANSITION METALS DICHALCOGENIDES, QUASI ONE-DIMENSIONAL STRUCTURES OF TRANSITION METALS AND OXIDES OF TRANSITION METALS | 520 |
| 23 | US20160145752 | Catalysts for Carbon Dioxide Conversion The disclosure relates generally to improved methods for the reduction of carbon dioxide. The disclosure relates more specifically to catalytic methods for electrochemical reduction of carbon... | 425 |
| 24 | WO/2016/100204A2 | CATALYST SYSTEM FOR ADVANCED METAL-AIR BATTERIES The disclosure relates generally to batteries. The disclosure relates more specifically to improved catalyst systems for metal-air batteries. A metal-air battery comprising: an anode comprising a... | 417 |
| 25 | US20150118487 | PLASMA-ASSISTED NANOFABRICATION OF TWO-DIMENSIONAL METAL CHALCOGENIDE LAYERS The invention describes two methods for manufacturing metal dichalcogenide materials. The invention also includes a coated dichalcogenide substrate. | 406 |
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