Full paper Bifunctional metal phosphide FeMnP films from single source metal organic chemical vapor deposition for efficient overall water splitting

Highlights • FeMnP was grown on Ni foam or graphene-wrapped Ni foam by MOCVD. • Films were grown using the single-source molecular precursor FeMn(CO) 8 (μ-PH(μ-PH 2 ). • The films are an efficient bifunctional electrocatalyst for water splitting. • FeMnP/graphene/Ni foam achieved a current density of 10 mA cm−2 at 1.55 V for overall water splitting. • DFT investigation supports the outstanding electrocatalytic activity of FeMnP. Abstract Developing stable and efficient bifunctional catalysts for overall water splitting into hydrogen and oxygen is a critical step in the realization of several clean-energy technologies. Here we report a robust and highly active electrocatalyst that is constructed by deposition of the ternary metal phosphide FeMnP onto graphene-protected nickel foam by metal-organic chemical vapor deposition from a single source precursor. FeMnP exhibits high electrocatalytic activity toward both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Utilizing FeMnP/GNF as both the anode and the cathode for overall water splitting, a current density of 10 mA cm−2 is achieved at a cell voltage of as low as 1.55 V with excellent stability. Complementary density functional theory (DFT) calculations suggest that facets exposing both Fe and Mn sites are necessary to achieve high HER activity. The present work provides a facile strategy for fabricating highly efficient electrocatalysts from earth-abundant materials for overall water splitting. Graphical abstract

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Keywords FeMnP MOCVD Bifunctional electrocatalyst Overall water splitting

Zhenhuan Zhao is currently a postdoc in Prof. Zhiming Wang’s group at the Institute of Frontier and Fundamental Sciences at the University of Electronic Sciences and Technology of China. He is also a postdoc fellow in Prof. Jiming Bao’s group at the Department of Electrical and Computer Engineering at the University of Houston. He received his PhD from Shandong University in 2015. His current research interests include the synthesis and characterization of nanomaterials for energy conversion in electrocatalysis, photocatalysis and photoelectrochemistry.

Desmond E. Schipper is a graduate student in the Department of Chemistry at Rice University. He received his BS in Biochemistry from UT-Austin where he worked with Richard Jones on high nuclearity, luminescent lanthanide metal complexes. He joined the Whitmire research group in 2013 and is the recipient of a National Science Foundation Graduate Research Fellowship. His research focuses on the synthesis and characterization of metal-pnictide cluster compounds for use as single-source precursors for advanced catalysts. He enjoys playing the piano.

Andrew P. Leitner is a Postdoctoral Research Associate working for Professor Kenton Whitmire at Rice University. Dr. Leitner received his Ph.D. in Inorganic Chemistry from the University of South Carolina in 2015. Since he joined the Whitmire lab he has helped to develop a methodology for the use of transition metal carbonyl clusters as single-source organometallic precursors in a chemical vapor deposition process to produce thin films of transition metal phosphides. His research interests are Inorganic Synthesis, Porous Materials and Energy Storage.

Hari Thirumalai is currently pursuing his Ph.D. in Chemical and Biomolecular Engineering under the supervision of Prof. Lars C. Grabow at the University of Houston. He completed is B.E in R.V. College of Engineering, Bangalore India, and his M.S in Chemical Engineering at Carnegie Mellon University, United States. His research interests span the theoretical modeling of processes on heterogeneous catalysts and electrocatalysts pertaining to energy applications using density functional theory and experimental transient kinetics using the Temporal Analysis of Products technique.

Dr. Jing-Han Chen received his Ph.D. in Applied Physics from Texas A&M University, College Station, Texas and then worked at Department of Chemistry, Rice University, Houston, Texas as a postdoctoral research associate. Since 2017, he has started his current postdoctoral researcher position at Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana. His research interests has focused mainly on understanding the phase transition nature of solid-state materials with emphasis upon their thermal behaviour and on developing magnetocaloric materials for magnetic refrigeration application by means of experimental methods as well as scientific computing approaches.

Lixin Xie received her B.S. degree in Polymetric Material and Engineering from Sun Yat-Sen University, PR China (2011) and M.S. degree in Material Science from University of Science and Technology of China, PR China (2014). She is currently a Ph.D. student in Dr. Shuo Chen's group. Her main research focuses on transmission electron microscopy and novel battery materials for energy storage.

Fan Qin is currently a Ph.D. student under the supervision of Prof. Jiming Bao in Materials Science & Engineering at the University of Houston. He obtained his bachelor and master degree from Wuhan Institute of Technology. His present research interests focus on the rational design of earth-abundant, high-efficient electrocatalysts and photocatalysts toward water splitting.

Md Kamrul Alam received his Bachelor Degree in Physics from University of Dhaka, Bangladesh and Master's Degree in Applied Physics from Texas Tech University, USA. He is currently a Ph.D. candidate under the supervision of Prof. Jiming Bao at Materials Science and Engineering, University of Houston, Texas, USA. His research interest is on 2D materials growth, characterization, and device fabrication. His research mainly focuses on Plasmonic properties of noble metals and graphene in the visible and infrared region.

Lars C. Grabow is an assistant professor of Chemical and Biomolecular Engineering and Chemistry at the University of Houston. He received his PhD from the University of Wisconsin – Madison, and continued his postdoctoral research at the Technical University of Denmark and Stanford University. His expertise is the application of electronic structure calculations and kinetic modeling to problems in heterogeneous catalysis. He received early career awards from DOE and NSF, is the Vice Chair of the AIChE Catalysis and Reaction Engineering division, and serves on the Early Career Advisory Board of ACS Catalysis, and the International Advisory Board of ChemCatChem.

Dr. Shuo Chen is currently an assistant professor in Department of Physics at the University of Houston. She obtained her B. S. in Physics from Peking University in China in 2002 and then Ph.D. in Physics from Boston College in 2006. From 2006 to 2011 she was a postdoctoral associate in the Department of Mechanical Engineering at MIT. Her research focuses on materials physics, especially synthesis and in situ electron microscopy of nanostructural materials for energy conversion and storage, such as thermoelectric materials, electrocatalysts, and batteries.

Dr. Dezhi Wang received his bachelor degree in 1984 and master degree in 1987 from Huazhong University of Science and Technology in materials science and engineering. He obtained his Ph.D. in 2007 from Boston College in Physics. Currently he is a research professor in the department of Physics and TcSUH at University of Houston and he was the electron microscope user facility manager and a research assistant professor at Boston College before he joined UH. His research focuses on nanostructure synthesis and characterization.

Dr. Zhifeng Ren is currently an M.D. Anderson Chair Professor in the Department of Physics and TcSUH at the University of Houston. He obtained his Ph.D. degree from the Institute of Physics Chinese Academy of Sciences in 1990, master degree from Huazhong University of Science and Technology in 1987, and bachelor degree from Sichuan Institute of Technology in 1984. He was a postdoc and research faculty at SUNY Buffalo (1990–1999) before joining BC as an Associate Professor in 1999. He specializes in thermoelectric materials, solar thermoelectric devices & systems, photovoltaic materials & systems, carbon nanotubes & semi-conducting nanostructures, nanocomposites, bio agent delivery & biosensors, flexible transparent conductors, superconductors, etc. He is a fellow of the APS and AAAS. Recently he was elected as a fellow of the National Academy of Inventors (NAI). He was recipient of the R&D 100 award in 2008 and the 2014 Edith & Peter O’Donnell Award in Science of The Academy of Medicine, Engineering, and Science of Texas.

Zhiming M. Wang received his B.S. degree in applied physics from Qingdao University, Qingdao, China, in 1992, his M.S. degree in physics from Beijing University in Beijing, China, in 1995, and his Ph.D. degree in condensed matter physics from the Institute of Semiconductors at the Chinese Academy of Sciences in Beijing, China, in 1998. Now he is a Professor of National 1000-Talent Program, working in the University of Electronic Science and Technology of China. His research has centered on the optoelectronic properties of low-dimensional semiconductor nanostructures and corresponding applications in photovoltaic devices.

Kenton H. Whitmire is Professor of Chemistry at Rice University in Houston, TX where he has been on faculty since 1982. He received his Ph.D. from Northwestern University, followed by a NATO Postdoctoral Fellowship in Cambridge (UK). He has been a recipient of an Alexander von Humboldt Research Award. His research interests include the synthesis, characterization and reactivity of inorganic and organometallic compounds including coordination compounds of the heavy main group elements and transition metal carbonyl clusters incorporating p-block elements, with a view to using these compounds to produce advanced nano materials that cannot be prepared by other methods.

Dr. Bao is an associate professor of Electrical and Computer engineering at the University of Houston. He graduated from Zhejiang University with B.S. and M.S. in physics in 1992 and 1995, respectively. He obtained his Ph.D. in applied physics in 2003 from the University of Michigan, he then did post-doctoral research at Harvard University before joining the University of Houston in 2008 as an assistant professor. His current research covers many interdisciplinary topics ranging from solar energy conversion to fiber optic sensing. More information can be found from Dr. Bao's group website at http://nano.ee.uh.edu/.

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