SusChEM: Collaborative Research: Atomic Level Properties of Nanoscale Metal Phosphide Catalysts for Heteroatom Removal Reactions

在这个由化学系化学催化计划资助的项目中，西华盛顿大学的Mark Bussell和Takele Seda教授、韦恩州立大学的Stephanie Brock教授和弗吉尼亚理工大学的S.Ted Oyama教授正在研究一种用于从石油和其他石油中去除杂质的新型材料的基本性质。这种新材料由与磷结合的金属组成，被称为金属磷化物，已被证明能够从石油和其他植物油或食品油中去除硫、氮和氧杂质。对这种脱除催化剂的需求很高，因为所有这些油都含有大量杂质，而且必须以符合严格环境标准的方式进行脱除。通过合作，该项目的研究人员正在探索颗粒大小、形状和组成对金属磷化物基本催化性能的影响，为这些有前途的催化剂的改进和商业化提供新的信息。基于金属磷化物的新一代催化剂的开发将对美国和全球产生积极的经济和环境影响。这个合作团队由一所以本科为主的机构的教员Pi Bussell和联席Pi Seda、一所城市研究型大学的联席教员Pi Brock以及在美国和日本大型研究型大学联合任职的联席Pi Oyama组成，成员广泛。参与该项目的教师和学生正在参与K-12外联活动，以教育和招聘下一代STEM人才，以解决世界面临的一系列能源问题。过渡金属磷化物具有作为高活性加氢脱硫(HDS)和加氢脱氧(HDO)催化剂的潜力。虽然金属磷化物是一种很有前途的新一代加氢处理催化剂，但在知道活性中心密度、表面组成和抗中毒/失活机理的影响之前，这种磷化物催化剂的改进和商业化前景面临着巨大的挑战。本项目的目的是确定颗粒大小、颗粒形状和组成在确定包裹在介孔氧化物壳层中的金属磷化物纳米颗粒在HDS和HDO反应中的活性和选择性方面的作用。正在研究预制颗粒，因为它们可以制备成尺寸在2-30 nm之间的近乎单分散的样品，也可以制备成球形或棒状单晶，从而能够量化活性中心密度(从而周转频率(TOF))以及评估不同晶面的相对活性。合作团队的每个成员都带来了独特的表征能力，以研究定义明确的金属磷化物纳米颗粒催化剂的结构细节。所提出的核壳纳米催化剂的研究活动将使我们能够探索金属磷化物上HDS和HDO的基本化学，为这些有前途的催化剂的改进和商业化提供新的信息。

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professors Mark Bussell and Takele Seda of Western Washington University, Professor Stephanie Brock of Wayne State University and Professor S. Ted Oyama of Virginia Tech are investigating the fundamental properties of a new class of materials for the removal of impurities from petroleum and other oils. The new materials, composed of metals bonded to phosphorus, are known as metal phosphides and have been shown capable of removing sulfur, nitrogen and oxygen impurities from both petroleum and other oils made from plant or food sources. The need for such removal catalysts is high because all these oils contain substantial impurities, and removing them must be done in such a way that stringent environmental standards are met. By working collaboratively, the researchers on this project are probing the role of particle size, shape and composition on the fundamental catalytic properties of metal phosphides, providing new information for the improvement and commercialization of these promising catalysts. The development of a new generation of catalysts based on metal phosphides would have positive economic and environmental impacts in the U.S. and globally. The collaborative team consisting of PI Bussell and co-PI Seda, faculty members at a predominantly undergraduate institution, co-PI Brock, a faculty member at an urban research university, and co-PI Oyama, who has joint appointments at large U.S. and Japanese research universities, embraces a diverse range of participants. The faculty and students involved in this project are participating in K-12 outreach to educate and recruit the next generation of STEM talent to address the range of energy issues facing the world. Transition metal phosphides have the potential to be highly active hydrodesulfurization (HDS) and hydrodeoxygenation (HDO) catalysts. While metal phosphides represent a promising next generation catalyst for hydrotreating applications, until the effects of active site density, surface composition, and mechanism of resistance to poisoning/deactivation are known, the prospects for improvement and commercialization of such phosphide catalysts face significant challenges. The aims of this project are to determine the roles of particle size, particle shape and composition in determining the activity and selectivity of metal phosphide nanoparticles encapsulated in mesoporous oxide shells for the HDS and HDO reactions. Pre-formed particles are being investigated because they can be prepared as nearly monodisperse samples in sizes ranging from 2-30 nm, and as spherical or rod-shaped single crystallites, thereby enabling quantification of the active site density (and thus turnover frequencies (TOFs)) as well as assessment of the relative activity of different crystal faces. Each member of the collaborative team brings unique characterization capabilities for investigating the structural details of the well-defined metal phosphide nanoparticle catalysts. The proposed research activities with core-shell nanocatalysts will allow us to probe the fundamental chemistry of HDS and HDO over metal phosphides, providing new information for the improvement and commercialization of these promising catalysts.