Screening of transition and post-transition metals to incorporate into copper oxide and copper bismuth oxide for photoelectrochemical hydrogen evolution

Abstract

A new dispenser and scanner system is used to create and screen Bi-M-Cu oxide arrays for cathodic photoactivity, where M represents 1 of 22 different transition and post-transition metals. Over 3000 unique Bi : M : Cu atomic ratios are screened. Of the 22 metals tested, 10 show a M-Cu oxide with higher photoactivity than CuO and 10 show a Bi-M-Cu oxide with higher photoactivity than CuBi2O4. Cd, Zn, Sn, and Co produce the most photoactive M-Cu oxides, all showing a 200-300% improvement in photocurrent over CuO. Ag, Cd, and Zn produce the highest photoactivity Bi-M-Cu oxides with a 200-400% improvement over CuBi2O4. Most notable is a Bi-Ag-Cu oxide (Bi : Ag : Cu atomic ratio of 22 : 3 : 11) which shows 4 times higher photocurrent than CuBi2O4. This material is capable of evolving hydrogen under illumination in neutral electrolyte solutions at 0.6 V vs. RHE when Pt is added to the surface as an electrocatalyst.

Efficient Solar‐Assisted O2 Reduction Using a Cofacial Iron Porphyrin Dimer Catalyst Integrated into a p‐CuBi2O4 Photocathode

“…The film thickness is approximately 2 μm (Figure S8 in the Supporting Information) and is highly compacted indicating its strong adhesion to the FTO electrode surface that is achieved by involving Mim in the preparation. X‐ray photoelectron spectroscopy (XPS, Figure S9 in the Supporting Information) measurements of the p‐CuBi 2 O 4 film showed the presence of Cu 2p 3/2 and Bi 4f 5/2 and 4f 7/2 peaks at 934.1, 163.8, and 158.5 eV, respectively . The energy‐dispersive spectroscopy (EDS) measurements (Figure S10 in the Supporting Information) confirmed the presence of Cu and Bi and O in the film.…”

“…These include electrodeposition/thermala nnealing method, [42,45,46] screen printing, [52] and drop-casting/heating method. [53] We recently developed a simple novel method involving an ethyl methyli midazolium triflate (EMI OTf) ionic liquid to prepare ah ighly mechanically stable thin film of water oxidation anode (CaMn-Oxide [54] )o r photoanode (BiVO 4 [55] )o nt he surface of FTO electrode. EMI OTf, however,i se xpensive and the need to replace it with a cheaper material is in high demand.…”

Recent Advances in Bismuth‐Based Nanomaterials for Photoelectrochemical Water Splitting

“…However,i ti sa lso observed that doping is not alwaysf avorable to enhance the water-splitting properties, as it can also become ar ecombination center. [162] Although the photocurrentc an be greatlye nhanced by doping with ad esired metal ion, the stabilityi ssue remains ac ritical challenge for PEC performance. Surprisingly,e xcept for BiVO 4 ,r eports on doping of metals or non-metals for other bismuth-based materials are rare.…”

Methods of photoelectrode characterization with high spatial and temporal resolution

“…Generally, high spatial resolution and ultrafast spectroscopy are not needed in these studies, and the reader is referred to other literature on the topic. 12,15,16,[23][24][25][26][27][28] The remainder of this paper provides an overview of in situ SPM techniques (Section 2), ultrafast spectroscopy techniques (Section 3), and computational tools (Section 4) that have been used, or have the potential to be used, for in situ investigation photoelectrodes with high spatial and/or temporal resolution. In addition to describing the basic principles behind each class of techniques, the opportunities and challenges for using these…”