美國(guó)威斯康星大學(xué)麥迪遜分校（UniversityofWisconsin-Madison）化學(xué)與生物工程學(xué)教授ManosMavrikakis和馬里蘭大學(xué)（UniversityofMaryland）化學(xué)與生物化學(xué)教授Bryan Eichhorn近日在《自然—材料學(xué)》網(wǎng)絡(luò)版上發(fā)表的論文中描述了一種新型催化劑,。它由被一層或兩層鉑原子包圍的釕納米顆粒組成，是一種高效的室溫催化劑,，可顯著改善關(guān)鍵的氫純化反應(yīng),，從而獲取更多的氫用于燃料電池的供能。目前,，全世界大多數(shù)氫的供應(yīng)來(lái)自于化石燃料,，這個(gè)過(guò)程稱作重整?？茖W(xué)家相信,，燃料電池不久就能通過(guò)由可再生能源得到的氫來(lái)進(jìn)行發(fā)電。這個(gè)過(guò)程的重要一步稱為PROX反應(yīng),，它是氫進(jìn)入燃料電池前,，利用催化劑去除其中的CO。CO的存在是燃料電池實(shí)際應(yīng)用的一個(gè)主要障礙,，因?yàn)樗净巳剂想姵胤磻?yīng)中昂貴的鉑催化劑,。
質(zhì)子交換膜燃料電池能夠替代應(yīng)用于運(yùn)輸工具中的其它電池，它通過(guò)利用多孔碳電極進(jìn)行發(fā)電,，電極中含有被固體聚合物分開(kāi)的鉑催化劑,。氫燃料進(jìn)入電池的一極，氧進(jìn)入另一極,，鉑催化劑促使氫分子中產(chǎn)生質(zhì)子,，這些質(zhì)子穿過(guò)膜與另一極的氧發(fā)生反應(yīng),，結(jié)果產(chǎn)生電以及副產(chǎn)品水和熱。傳統(tǒng)的釕,、鉑催化劑結(jié)合必須達(dá)到70℃才能發(fā)生PROX反應(yīng),，但相同的元素以核殼納米顆粒結(jié)構(gòu)結(jié)合后，能夠使反應(yīng)在室溫下就發(fā)生,。催化劑活化反應(yīng)物以及得到產(chǎn)物的溫度越低,，節(jié)約的能量就越多。產(chǎn)生這種室溫反應(yīng)的原因有兩個(gè),，首先是催化劑的核殼結(jié)構(gòu),，與單純的鉑催化劑相比，這種特別的結(jié)構(gòu)核成分能夠使表面吸收較少的CO,，給氧進(jìn)入并發(fā)生反應(yīng)留下空間,。另一個(gè)原因是新的反應(yīng)機(jī)理，利用氫原子結(jié)合氧分子并生成氫過(guò)氧基,，這樣很容易生成氧原子。氧原子與CO結(jié)合生成二氧化碳CO2,，這樣留下更多的氫分子供給燃料電池,。這項(xiàng)突破對(duì)于發(fā)展燃料電池技術(shù)有著重要意義，甚至對(duì)催化劑本身的發(fā)展也會(huì)產(chǎn)生重大影響,。（科學(xué)網(wǎng)）
生物谷推薦原始出處：
Nature Materials 7, 333 - 338 (2008)
Published online: 16 March 2008 | doi:10.1038/nmat2156
Subject Categories: Catalytic materials | Materials for energy | Nanoscale materials
Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen
Selim Alayoglu1, Anand U. Nilekar2, Manos Mavrikakis2 & Bryan Eichhorn1
Abstract
Most of the world's hydrogen supply is currently obtained by reforming hydrocarbons. 'Reformate' hydrogen contains significant quantities of CO that poison current hydrogen fuel-cell devices. Catalysts are needed to remove CO from hydrogen through selective oxidation. Here, we report first-principles-guided synthesis of a nanoparticle catalyst comprising a Ru core covered with an approximately 1–2-monolayer-thick shell of Pt atoms. The distinct catalytic properties of these well-characterized core–shell nanoparticles were demonstrated for preferential CO oxidation in hydrogen feeds and subsequent hydrogen light-off. For H2 streams containing 1,000 p.p.m. CO, H2 light-off is complete by 30 °C, which is significantly better than for traditional PtRu nano-alloys (85 °C), monometallic mixtures of nanoparticles (93 °C) and pure Pt particles (170 °C). Density functional theory studies suggest that the enhanced catalytic activity for the core–shell nanoparticle originates from a combination of an increased availability of CO-free Pt surface sites on the Ru@Pt nanoparticles and a hydrogen-mediated low-temperature CO oxidation process that is clearly distinct from the traditional bifunctional CO oxidation mechanism.
