skip to main content

Title: Bipolar membrane polarization behavior with systematically varied interfacial areas in the junction region
The palette of applications for bipolar membranes (BPMs) has expanded recently beyond electrodialysis as they are now being considered for fuel cell and electrolysis applications. Their deployment in emerging electrochemical technologies arises from the need to have a membrane separator that provides disparate pH environments and to prevent species crossover. Most materials research for BPMs has focused on water dissociation catalysts and less emphasis has been given to the design of the polycation–polyanion interface for improving BPM performance. Here, soft lithography fabricated a series of micropatterned BPMs with precise control over the interfacial area in the bipolar junction. Polarization experiments showed that a 2.28× increase in interfacial area led to a 250 mV reduction in the onset potential. Additionally, the same increase in interfacial area yielded marginal improvements in current density due to the junction region being under kinetics-diffusion control. A simple physics model based on the electric field of the junction region rationalized the reduction in the overpotential for water dissociation as a function of interfacial area. Finally, the soft lithography approach was also conducive for fabricating BPMs with different chemistries ranging from perfluorinated polymer backbones to alkaline stable poly(arylene) hydrocarbon polymers. These polymer chemistries are better suited for more » fuel cell and electrolysis applications. The BPM featuring the alkaline stable poly(terphenyl) anion exchange membrane had an onset potential of 0.84 V, which was near the thermodynamic limit, and was about 150 mV lower than a commercially available variant. « less
; ; ; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
Journal of Materials Chemistry A
Sponsoring Org:
National Science Foundation
More Like this
  1. Catalyzing water dissociation (WD) into protons and hydroxide ions is important both for fabricating bipolar membranes (BPMs) that can couple different pH environments into a single electrochemical device and for accelerating electrocatalytic reactions that consume protons in neutral to alkaline media. We designed a BPM electrolyzer to quantitatively measure WD kinetics and show that, for metal nanoparticles, WD activity correlates with alkaline hydrogen evolution reaction activity. By combining metal-oxide WD catalysts that are efficient near the acidic proton-exchange layer with those efficient near the alkaline hydroxide-exchange layer, we demonstrate a BPM driving WD with overpotentials of <10 mV at 20 mA·cm−2and pure water BPM electrolyzers that operate with an alkaline anode and acidic cathode at 500 mA·cm−2with a total electrolysis voltage of ~2.2 V.

  2. The alkaline hydrogen evolution reaction (A-HER) holds great promise for clean hydrogen fuel generation but its practical utilization is severely hindered by the sluggish kinetics for water dissociation in alkaline solutions. Traditional ways to improve the electrochemical kinetics for A-HER catalysts have been focusing on surface modification, which still can not meet the demanding requirements for practical water electrolysis because of catalyst surface deactivation. Herein, we report an interior modification strategy to significantly boost the A-HER performance. Specifically, a trace amount of Pt was doped in the interior Co 2 P (Pt–Co 2 P) to introduce a stronger dopant–host interaction than that of the surface-modified catalyst. Consequently, the local chemical state and electronic structure of the catalysts were adjusted to improve the electron mobility and reduce the energy barriers for hydrogen adsorption and H–H bond formation. As a proof-of-concept, the interior-modified Pt–Co 2 P shows a reduced onset potential at near-zero volts for the A-HER, low overpotentials of 2 mV and 58 mV to achieve 10 and 100 mA cm −2 , and excellent durability for long-term utilization. The interior-modified Pt–Co 2 P delivers superior A-HER performance to Pt/C and other state-of-the-art electrocatalysts. This work will open a new avenuemore »for A-HER catalyst design.« less
  3. Water electrolysis using renewable energy inputs is being actively pursued as a green route for hydrogen production. However, it is limited by the high energy consumption due to the sluggish anodic oxygen evolution reaction (OER) and safety issues associated with H2 and O2 mixing. Here, we replaced OER with an electrocatalytic oxidative dehydrogenation (EOD) of aldehydes for bipolar H2 production and achieved industrial-level current densities at cell voltages much lower than during water electrolysis. Experimental and computational studies suggest a reasonable barrier for C-H dissociation on Cu surfaces, mainly through a diol intermediate, with a potential-dependent competition with the solution-phase Cannizzaro reaction. The kinetics of EOD reaction was further enhanced by a porous CuAg catalyst prepared from a galvanic replacement method. Through Ag incorporation and its modification of the Cu surface, the geometric current density and electrocatalyst durability were significantly improved. Finally, we engineered a bipolar H2 production system in membrane-electrode assembly-based flow cells to facilitate mass transport, achieving a maximum current density of 248 and 390 mA cm−2 at cell voltages of 0.4 V and 0.6 V, respectively. The faradaic efficiency of H2 from both cathode and anode reactions both attained ~100%. Taking advantage of the bipolar H2 productionmore »without the issues associated with H2/O2 mixing, an inexpensive, easy-to-manufacture dialysis porous membrane was demonstrated to substitute the costly anion exchange membrane, achieving an energy-efficient and cost-effective process in a simple reactor for H2 production. The estimated H2 price of $2.51/kg from an initial technoeconomic assessment is competitive with US DoE’s “Green H2” targets.« less
  4. Energy harvesting from solar and water has created ripples in materials energy research for the last several decades, complemented by the rise of Hydrogen as a clean fuel. Among these, water electrolysis leading to generation of oxygen and hydrogen, has been one of the most promising routes towards sustainable alternative energy generation and storage, with applications ranging from metal-​air batteries, fuel cells, to solar-​to-​fuel energy conversion systems. In fact, solar water splitting is one of the most promising method to produce Hydrogen without depleting fossil-​fuel based natural resources. However, the efficiency and practical feasibility of water electrolysis is limited by the anodic oxygen evolution reaction (OER)​, which is a kinetically sluggish, electron-​intensive uphill reaction. A slow OER process also slows the other half- cell reaction, i.e. the hydrogen evolution reaction (HER) at the cathode. Hence, designing efficient catalysts for OER process from earth-​abundant resources has been one of the primary concerns for advancing solar water splitting. In the Nath group we have focused on transition metal chalcogenides as efficient OER electrocatalysts. We have proposed the idea that these chalcogenides, specifically, selenides and tellurides will show much better OER catalytic activity due to increasing covalency around the catalytically active transition metalmore »site, compared to the oxides caused by decreasing electronegativity of the anion, which in turn leads to variation of chem. potential around the transition metal center, [e.g. lowering the Ni 2+ -​-​> Ni 3+ oxidn. potential in Ni-​based catalysts where Ni 3+ is the actually catalytically active species]​. Based on such hypothesis, we have synthesized a plethora of transition metal selenides including those based on Ni, Ni-​Fe, Co, and Ni-​Co, which show high catalytic efficiency characterized by low onset potential and overpotential at 10 mA​/cm 2 [Ni 3 Se 2 - 200 - 290 mV; Co 7 Se 8 - 260 mV; FeNi 2 Se 4 -​NrGO - 170 mV (NrGO - N-​doped reduced graphene oxide)​; NiFe 2 Se 4 - 210 mV; CoNi 2 Se 4 - 190 mV; Ni 3 Te 2 - 180 mV]​.« less
  5. Metal-mediated cross-coupling reactions offer organic chemists a wide array of stereo- and chemically-selective reactions with broad applications in fine chemical and pharmaceutical synthesis.1 Current batch-based synthesis methods are beginning to be replaced with flow chemistry strategies to take advantage of the improved consistency and process control methods offered by continuous flow systems.2,3 Most cross-coupling chemistries still encounter several issues in flow using homogeneous catalysis, including expensive catalyst recovery and air sensitivity due to the chemical nature of the catalyst ligands.1 To mitigate some of these issues, a ligand-free heterogeneous catalysis reaction was developed using palladium (Pd) loaded into a polymeric network of a silicone elastomer, poly(hydromethylsiloxane) (PHMS), that is not air sensitive and can be used with mild reaction solvents (ethanol and water).4 In this work we present a novel method of producing soft catalytic microparticles using a multiphase flow-focusing microreactor and demonstrate their application for continuous Suzuki-Miyaura cross-coupling reactions. The catalytic microparticles are produced in a coaxial glass capillary-based 3D flow-focusing microreactor. The microreactor consists of two precursors, a cross-linking catalyst in toluene and a mixture of the PHMS polymer and a divinyl cross-linker. The dispersed phase containing the polymer, cross-linker, and cross-linking catalyst is continuously mixed and thenmore »formed into microdroplets by the continuous phase of water and surfactant (sodium dodecyl sulfate) introduced in a counter-flow configuration. Elastomeric microdroplets with a diameter ranging between 50 to 300 micron are produced at 25 to 250 Hz with a size polydispersity less than 3% in single stream production. The physicochemical properties of the elastomeric microparticles such as particle swelling/softness can be tuned using the ratio of cross-linker to polymer as well as the ratio of polymer mixture to solvent during the particle formation. Swelling in toluene can be tuned up to 400% of the initial particle volume by reducing the concentration of cross-linker in the mixture and increasing the ratio of polymer to solvent during production.5 After the particles are produced and collected, they are transferred into toluene containing palladium acetate, allowing the particles to incorporate the palladium into the polymer network and then reduce the palladium to Pd0 with the Si-H functionality present on the PHMS backbones. After the reduction, the Pd-loaded particles can be washed and dried for storage or switched into an ethanol/water solution for loading into a micro-packed bed reactor (µ-PBR) for continuous organic synthesis. The in-situ reduction of Pd within the PHMS microparticles was confirmed using energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and focused ion beam-SEM, and TEM techniques. In the next step, we used the developed µ-PBR to conduct continuous organic synthesis of 4-phenyltoluene by Suzuki-Miyaura cross-coupling of 4-iodotoluene and phenylboronic acid using potassium carbonate as the base. Catalyst leaching was determined to only occur at sub ppm concentrations even at high solvent flow rates after 24 h of continuous run using inductively coupled plasma mass spectrometry (ICP-MS). The developed µ-PBR using the elastomeric microparticles is an important initial step towards the development of highly-efficient and green continuous manufacturing technologies in the pharma industry. In addition, the developed elastomeric microparticle synthesis technique can be utilized for the development of a library of other chemically cross-linkable polymer/cross-linker pairs for applications in organic synthesis, targeted drug delivery, cell encapsulation, or biomedical imaging. References 1. Ruiz-Castillo P, Buchwald SL. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions. Chem Rev. 2016;116(19):12564-12649. 2. Adamo A, Beingessner RL, Behnam M, et al. On-demand continuous-flow production of pharmaceuticals in a compact, reconfigurable system. Science. 2016;352(6281):61 LP-67. 3. Jensen KF. Flow Chemistry — Microreaction Technology Comes of Age. 2017;63(3). 4. Stibingerova I, Voltrova S, Kocova S, Lindale M, Srogl J. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity. Org Lett. 2016;18(2):312-315. 5. Bennett JA, Kristof AJ, Vasudevan V, Genzer J, Srogl J, Abolhasani M. Microfluidic synthesis of elastomeric microparticles: A case study in catalysis of palladium-mediated cross-coupling. AIChE J. 2018;0(0):1-10.« less