Capabilities

Capabilities

Photoelectrochemical Device In Situ and Operando Testing Using X-Rays

Laboratory

Lawrence Berkeley National Laboratory (LBNL)

Capability Expert

Walter Drisdell, David Prendergast, Ethan Crumlin, Jinghua Guo, Miquel Salmeron

Class

Characterization

Node Readiness Category

1: High-Temperature Electrolysis (HTE)
1: Low-Temperature Electrolysis (LTE)
1: Photoelectrochemical (PEC)
1: Solar Thermochemical (STCH)

Description

The Advanced Light Source has developed two facilities for in situ and operando characterization of electrolyte-photoelectrode interfaces in a photolectrochemical cell in collaboration with JCAP and several battery programs. One is based on a tender x-rays (2-5KeV) endstation that is not available to general users but can be accessed through collaborations. It is capable of x-ray photoemission measurements of species in the interfacial region between an electrode or photoelectrode and acid or base electrolyte, in the dark or under visible illumination. The electrochemical cell is held near atmospheric pressure, and electrons are collected through a differentially pumped lens system. This capability also includes relevant ab-initio modeling of the experimental data to provide more complete understanding. The other facility is based on an electrochemical cell with x-ray transparent SiN membranes that separate the electrolyte from the endstation vacuum chamber. The sample is deposited on the solution side of the membrane. By collecting the electron yield current from the sample to ground absorption spectra of the interfacial double-layer species can be obtained under potentiostat control.

Capability Bounds‎

Sample sizes up to 1cm can be accommodated in the first, and thin films of metals and oxides in the second.

Unique Aspects‎

These are unique facilities that enable detailed studies of the chemistry and energetics of interfaces to be measured under bias. Strongly coupled combination of experimental and theoretical interpretation and expertise.

Availability‎

Facility is in use for JCAP's program as well as other programs. Access would be through JCAP collaboration. It is possible that additional time can be requested from the ALS for EMN related work. Computational work requires collaboration but is available.

Benefit‎

This capability is of use for evaluating the electrochemical operation of new materials combinations for photoelectrochemical water splitting devices.

Images

The cartoons show schematically the two set-ups. In the first (left) the reference, working and counter electrodes are immersed in a beaker containing electrolyte. The working electrode is immersed to establish a meniscus, and photoelectron spectra are measured through it. In the second (right) the electrodes are inside the cell, which as a small volume of a few mm3.

Left: The dynamic physiochemical response of a functioning graphene-based aerogel supercapacitor is monitored in operando by soft X-ray spectroscopy and interpreted through ab initio atomistic simulations. Unanticipated changes in the electronic structure of the electrode as a function of applied voltage bias indicate structural modifications across multiple length scales via independent pseudocapacitive and electric double layer charge storage channels. Right: The structure (average orientation) of water molecules in NaCl, and H2SO4 solutions on Au is determined from the operando XAS and

References‎

Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy, Michael F. Lichterman, Shu Hu, Matthias H. Richter, Ethan J. Crumlin, Stephanus Axnanda, Marco Favaro, Walter Drisdell, Zahid Hussain, Thomas Mayer, Bruce S. Brunschwig, Nathan S. Lewis, Zhi Liu and Hans-Joachim Lewerenz, Energy Environ. Sci. 2015, 8, 2409.
Ambient-Pressure XPS Study of a Ni–Fe Electrocatalyst for the Oxygen Evolution Reaction. Ali-Löytty, Harri; Louie, Mary W.; Singh, Meenesh R.; Li, Lin; Sanchez Casalongue, Hernan G.; Ogasawara, Hirohito; Crumlin, Ethan J.; Liu, Zhi; Bell, Alexis T.; Nilsson, Anders; Friebel, Daniel. The Journal of Physical Chemistry C, 120 (2016) 2247-225.3.
Operando Analyses of Solar Fuels Light Absorbers and Catalysts. Lewerenz, Hans-Joachim; Lichterman, Michael F.; Richter, Matthias H.; Crumlin, Ethan J.; Hu, Shu; Axnanda, Stephanus; Favaro, Marco; Drisdell, Walter; Hussain, Zahid; Brunschwig, Bruce S.; Liu, Zhi; Nilsson, Anders; Bell, Alexis T.; Lewis, Nathan S.; Friebel, Daniel. Electrochimica Acta 2016. http://dx.doi.org/10.1016/j.electacta.2016.06.006.
Detecting the oxyl radical of photocatalytic water oxidation at an n-SrTiO3/aqueous interface through its subsurface vibration David M. Herlihy, Matthias M. Waegele, Xihan Chen, C. D. Pemmaraju, David Prendergast, Tanja Cuk, Nature Chemistry 8, (2016) 549–555.
Potential-Induced Electronic Structure Changes in Supercapacitor Electrodes Observed by In Operando Soft X-Ray Spectroscopy. Michael Bagge-Hansen, Brandon C. Wood, Tadashi Ogitsu, Trevor M. Willey, Ich C. Tran, Arne Wittstock, Monika M. Biener, Matthew D. Merrill, Marcus A. Worsley, Minoru Otani, Cheng-Hao Chuang, David Prendergast, Jinghua Guo, Theodore F. Baumann, Tony van Buuren, Jurgen Biener and Jonathan R. I. Lee, Advanced Materials 27, 1512 (2015).
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy. Juan-Jesus Velasco-Velez, Cheng Hao Wu, Tod A. Pascal, Liwen F. Wan, Jinghua Guo, David Prendergast, Miquel Salmeron, Science 346, 831 (2014).
Atomic Scale Perspective of Ultrafast Charge Transfer at a Dye-Semiconductor Interface. Katrin R. Siefermann, Chaitanya D. Pemmaraju, Stefan Neppl, Andrey Shavorskiy, Amy A. Cordones, Josh Vura-Weis, Daniel S. Slaughter, Felix P. Sturm, Fabian Weise, Hendrik Bluhm, Matthew L. Strader, Hana Cho, Ming-Fu Lin, Camila Bacellar, Champak Khurmi, Jinghua Guo, Giacomo Coslovich, Joseph S. Robinson, Robert A. Kaindl, Robert W. Schoenlein, Ali Belkacem, Daniel M. Neumark, Stephen R. Leone, Dennis Nordlund, Hirohito Ogasawara, Oleg Krupin, Joshua J. Turner, William F. Schlotter, Michael R. Holmes, Marc Messerschmidt, Michael P. Minitti, Sheraz Gul, Jin Z. Zhang, Nils Huse, David Prendergast, and Oliver Gessner, J. Phys. Chem. Lett. 5, 2753 (2014).
Electronic structure of aqueous borohydride: a potential hydrogen storage medium. Andew M. Duffin, Alice H. England, Craig P. Schwartz, Janel S. Uejio, Gregory C. Dallinger, Orion Shih, David Prendergast, and Richard J. Saykally, Physical Chemistry Chemical Physics 13, 17077 (2011).
In-situ XAS investigation of the electrochemical reactions of graphene in aqueous electrolyte. Juan J. Velasco-Velez, Cheng-Hao Chuang, Camille Martinez, Inigo Martin-Fernandez, Hui-Ling Han, Way-Faung Pong, Yuen-Ron Shen, Yuegang Zhang, Jinghua Guo, and Miquel Salmeron. J. Electrochem. Soc. 160 (9) C445-C450 (2013).
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy. J. J. Velasco-Velez, C. H. Wu, Tod A. Pascal, L. F. Wan, J.-H. Guo, David Prendergast, and Miquel B. Salmeron. Science. 346, 831-834 (2014). DOI: 10.1126/science.1259437.
Photoelectron Spectroscopy at the graphene-liquid interface reveals electrodeposition of reduced cobalt in aqueous solutions. J.-J. Velasco-Velez, V. Pfeifer, M. Hävecker, R. Weatherup, R. Arrigo, C. H. Chuang, E. Stotz, G. Weinberg, M. B. Salmeron, R. Schlögl and A. Knop-Gericke. Angewandte Chem. Int. Ed. 54,14554-14558 (2015).