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At least 613 records · Page 34

The current status of high temperature electrochemistry-based CO 2 transport membranes and reactors for direct CO 2 capture and conversion

The concept of direct CO 2 capture and conversion has attracted significant interest from industries and academia in recent decades due to its potential to address the current grand challenge of global warming/climate change, rapid depletion of fossil fuels and realization of a future carbon neutral ecosystem. The incumbent benchmark technology for CO 2 capture is the post-combustion flue-gas “amine washing”, which is energy intensive and costly for large-scale commercial implementation. The CO 2 conversion technologies, on the other hand, are still at their infancy with many technical challenges to overcome, but primarily being explored in laboratory-scale, low-temperature, solution-based and high-temperature, solid-oxide-based electrochemical cells with renewable electricity perceived as the energy input. In this article, we provide a comprehensive overview on an emergent class of high-temperature electrochemical CO 2 transport membranes that can capture and convert CO 2 into valuable chemicals in single catalytic reactor fashion. The review starts with the chemistry and transport theory of three basic types of membranes purposely designed for different CO 2 feedstocks and downstream conversions. A range of key functional materials used in these membranes and their microstructural/electrochemical properties important to the CO 2 transport are then thoroughly discussed in conjunction with the effects of surface modifications and operating conditions. Several types of combined CO 2 capture and conversion catalytic reactors based on these membranes are also assessed with a focus on their working principles, system configurations and performance demonstrations. Finally, challenges and prospective of these electrochemical CO 2 transport membranes and their associated conversion reactors are candidly discussed for future development.

10 SYNTHETIC FUELS↗

Investigating the durability of a direct methanol fuel cell equipped with commercial Platinum Group Metal-free cathodic electro-catalysts

For the first time a long-term (500 h) durability study in direct methanol fuel cells (DMFCs) is carried out on a Platinum Group Metal-free (PGM-free) cathodic electro-catalyst commercially available on market. The electro-catalyst is tested for 500 h at a fixed cell voltage (0.3 V), recording the polarization curves during the operation. A drastic decrease in performance is observed after the first 100 h (from 220 to 75 mA cm –2 ); afterwards, the decrease is flatter, passing from 75 to 25 mA cm –2 (at 500 h). The causes of this performance degradation are investigated by postmortem physicochemical analyzes, such as X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with X-ray energy dispersive analysis (EDX). Finally, possible reasons of degradation are indicated to be PGM-free catalyst aggregation, carbon and nitrogen species decrease, Ruthenium dissolution and migration from the anode to the cathode, poisoning both membrane and cathode catalyst.

25 ENERGY STORAGE↗

Carbon nanotube porin diffusion in mixed composition supported lipid bilayers

Carbon nanotube porins (CNTPs), short pieces of carbon nanotubes capable of self-inserting into a lipid bilayer, represent a simplified model of biological membrane channels. We have used high-speed atomic force microscopy (HS-AFM) and all-atom molecular dynamics (MD) simulations to study the behavior of CNTPs in a mixed lipid membrane consisting of DOPC lipid with a variable percentage of DMPC lipid added to it. HS-AFM data reveal that the CNTPs undergo diffusive motion in the bilayer plane. Motion trajectories extracted from the HS-AFM movies indicate that CNTPs exhibit diffusion coefficient values broadly similar to values reported for membrane proteins in supported lipid bilayers. The data also indicate that increasing the percentage of DMPC leads to a marked slowing of CNTP diffusion. MD simulations reveal a CNTP-lipid assembly that diffuses in the membrane and show trends that are consistent with the experimental observations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Design and testing of a unique randomized gravity, continuous flow bioreactor

A rotating, null gravity simulator, or Couette bioreactor was successfully used for the culture of mammalian cells in a simulated microgravity environment. Two limited studies using Lipomyces starkeyi and Streptomyces clavuligerus were also conducted under conditions of simulated weightlessness. Although these studies with microorganisms showed promising preliminary results, oxygen limitations presented significant limitations in studying the biochemical and cultural characteristics of these cell types. Microbial cell systems such as bacteria and yeast promise significant potential as investigative models to study the effects of microgravity on membrane transport, as well as substrate induction of inactive enzyme systems. Additionally, the smaller size of the microorganisms should further reduce the gravity induced oscillatory particle motion and thereby improve the microgravity simulation on earth. Focus is on the unique conceptual design, and subsequent development of a rotating bioreactor that is compatible with the culture and investigation of microgravity effects on microbial systems. The new reactor design will allow testing of highly aerobic cell types under simulated microgravity conditions. The described reactor affords a mechanism for investigating the long term effects of reduced gravity on cellular respiration, membrane transfer, ion exchange, and substrate conversions. It offers the capability of dynamically altering nutrients, oxygenation, pH, carbon dioxide, and substrate concentration without disturbing the microgravity simulation, or Couette flow, of the reactor. All progeny of the original cell inoculum may be acclimated to the simulated microgravity in the absence of a substrate or nutrient. The reactor has the promise of allowing scientists to probe the long term effects of weightlessness on cell interactions in plants, bacteria, yeast, and fungi. The reactor is designed to have a flow field growth chamber with uniform shear stress, yet transfer high concentrations of oxygen into the culture medium. The system described allows for continuous, on line sampling for production of product without disturbing fluid and particle dynamics in the reaction chamber. It provides for the introduction of substrate, or control substances after cell adaptation to simulated microgravity has been accomplished. The reactor system provides for the nondisruptive, continuous flow replacement of nutrient and removal of product. On line monitoring and control of growth conditions such as pH and nutrient status are provided. A rotating distribution valve allows cessation of growth chamber rotation, thereby preserving the simulated microgravity conditions over longer periods of time.

Lassiter, Carroll B.↗

Highly Porous Polyimide Gel for Use as Battery Separator with Room Temperature Ionic Liquid Electrolytes

Advanced aerospace vehicular concepts require advances in many existing technologies, including space power and energy storage systems. Batteries represent one of the major areas in need of improvement, both in terms of energy density and safety, with growing concerns over the fire safety of commercial lithium-ion batteries. This has prompted efforts to develop nonflammable battery components, namely the electrolyte and separator. Existing commercial lithium-ion batteries utilize polyolefin microporous membranes as separators with an electrolyte consisting of a lithium salt dissolved in a mixture of cyclic carbonate solvents. This separator/electrolyte combination has ionic conductivities in the range of 10 −2 to 10 −3 S/cm. However, the cyclic carbonate solvents are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative. They offer good ionic conductivities and are inherently nonvolatile and nonflammable, giving them a safety advantage. However, many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Alternative separator materials, such as polyimides, are non-flammable and are capable of accepting RTILs into their structure. Polyimide gels, with a composition of 4,4′-oxydianiline, 3,3′,4,4′-tetracarboxylic dianhydride and cross-linked with Desmodur N3300A, possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85% porosity) for lithium-ion transport and conduction, as well as good mechanical properties. Furthermore, these polyimide gels are compatible with selected imidazolium-based RTILs. Nonflammable separator/electrolyte systems with room-temperature conductivities in the range of 10 −3 S/cm have been evaluated. It has been demonstrated that 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was the most promising among six RTILs screened, in terms of both ionic conductivity and constant current cycling.

Polyimide↗

Electrochemical characterization of evolving ionomer/electrocatalyst interactions throughout accelerated stress tests

Here, the degradation of polymer electrolyte membrane fuel cells (PEMFCs) catalyst layers used for heavy-duty vehicles was examined using a catalyst-specific accelerated stress test (AST). High surface area carbon supported dispersed Pt (Pt/HSC), annealed Pt (a-Pt/HSC) and PtCo (PtCo/HSC) alloy catalysts were examined over the course of 90,000 cycles by measuring changes in mass activity, O 2 transport resistance, electrochemical active surface area (ECSA), catalyst accessibility and ionomer-electrocatalyst interactions. Compared to a-Pt/HSC and Pt/HSC catalyst, the PtCo/HSC showed better initial mass activity, a larger initial mass transport loss, and faster degradation after the first 30k AST cycles, as a large portion of Co leached out during potential cycling. Pt/HSC showed higher initial performance relative to a-Pt/HSC but had faster degradation. STEM characterizations show that the ECSA losses are largely related to Pt dissolution resulting in either catalyst particle growth via the Ostwald ripening mechanism or redeposition in the membrane. Catalyst accessibility measurements showed decreased RH sensitivity for all three samples, while CO impedance measurements revealed a decrease in both Pt-water and carbon-water interactions. This implies that, Pt is either preferentially redepositing on the exterior of the carbon support, or that the ionomer is undergoing morphological changes enabling the enhanced intrusion of mesopores.

25 ENERGY STORAGE↗

Inverse Consequences of the SnO 2 Protection Layers on Pt/C Catalysts in Proton-Exchange Membrane Fuel Cells

Proton-exchange membrane fuel cells (PEMFCs) are promising energy-conversion systems, offering an appealing blend of high energy efficiency and low environmental impact. However, carbon corrosion of PEMFCs is known to significantly degrade their performance, remaining a critical challenge to overcome. In this study, we applied a Nb-doped SnO 2 (Nb-SnO 2 ) nanoparticle coating on Pt/C catalysts as a protective layer, with the Sn/C ratio in the precursors varying from 0.25:1 to 2.0:1. Contradictory behaviors of the coated Pt/C catalysts were observed at different Sn/C ratios. The Sn/C = 1.0 sample exhibited improved electrochemically active surface area retention after 500 cycles of accelerated stress testing (AST) but with more significant polarization and resistance increase observed in the polarization curves. In addition, agglomeration of Nb-SnO 2 particles was observed at a higher Sn/C ratio in the AST of a membrane electrode assembly, with less shrinkage of the total thickness of the Nb-SnO 2 -coated Pt/C electrode. We speculate that formation of Nb-SnO 2 agglomerates occurs once the protective layer is broken down or the unprotected carbon surface is corroded and that these Nb-SnO 2 agglomerates increase the tortuosity of the electron pathways and significantly increase the cell polarization.

30 DIRECT ENERGY CONVERSION↗

MoS 2 nanosheet integrated electrodes with engineered 1T-2H phases and defects for efficient hydrogen production in practical PEM electrolysis

Low electrical conductivity and poor accessibility of MoS 2 reaction sites raise great challenges in maximizing the triple-phase-boundary (TPB) sites of MoS 2 -based electrodes and minimizing ohmic losses for efficient hydrogen evolution reaction (HER) in practical proton exchange membrane (PEM) water electrolysis. Herein, we report a scalable hydrothermal approach to fabricate ionomer-free integrated electrodes with engineered 1 T-2 H heterophase and defect-rich MoS 2 nanosheets (MoS 2 NSs) in-situ grown onto the carbon fiber paper (CFP). With an ultralow loading of 0.14 mg/cm 2 , a small voltage of 2.25 V was obtained at 2000 mA/cm 2 in a practical cell with Nafion115 membrane, which outperforms all previously reported high-loading non-precious catalyst-based electrodes. Impressively, it shows 44 times higher mass activity than a high-loading and ionomer-mixed MoS 2 assemblies electrode. Furthermore, this work builds a bridge from catalyst optimization to electrode fabrication and provides a promising direction for improving intrinsic catalytic activity, electrode conductivity and stability for practical PEM water electrolysis.

1T-2H heterophase↗

NASA Tech Briefs, April 2003

Topics include: Tool for Bending a Metal Tube Precisely in a Confined Space; Multiple-Use Mechanisms for Attachment to Seat Tracks; Force-Measuring Clamps; Cellular Pressure-Actuated Joint; Block QCA Fault-Tolerant Logic Gates; Hybrid VLSI/QCA Architecture for Computing FFTs; Arrays of Carbon Nanotubes as RF Filters in Waveguides; Carbon Nanotubes as Resonators for RF Spectrum Analyzers; Software for Viewing Landsat Mosaic Images; Updated Integrated Mission Program; Software for Sharing and Management of Information; Optical-Quality Thin Polymer Membranes; Rollable Thin Shell Composite-Material Paraboloidal Mirrors; Folded Resonant Horns for Power Ultrasonic Applications; Touchdown Ball-Bearing System for Magnetic Bearings; Flux-Based Deadbeat Control of Induction-Motor Torque; Block Copolymers as Templates for Arrays of Carbon Nanotubes; Throttling Cryogen Boiloff To Control Cryostat Temperature; Collaborative Software Development Approach Used to Deliver the New Shuttle Telemetry Ground Station; Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers; and Time-Resolved Measurements in Optoelectronic Microbioanal.

Source record↗

Whole-soil warming decreases abundance and modifies the community structure of microorganisms in the subsoil but not in surface soil

Abstract. The microbial community composition in subsoils remains understudied, and it is largely unknown whether subsoil microorganisms show a similar response to global warming as microorganisms at the soil surface do. Since microorganisms are the key drivers of soil organic carbon decomposition, this knowledge gap causes uncertainty in the predictions of future carbon cycling in the subsoil carbon pool (> 50 % of the soil organic carbon stocks are below 30 cm soil depth). In the Blodgett Forest field warming experiment (California, USA) we investigated how +4 ∘C warming in the whole-soil profile to 100 cm soil depth for 4.5 years has affected the abundance and community structure of microorganisms. We used proxies for bulk microbial biomass carbon (MBC) and functional microbial groups based on lipid biomarkers, such as phospholipid fatty acids (PLFAs) and branched glycerol dialkyl glycerol tetraethers (brGDGTs). With depth, the microbial biomass decreased and the community composition changed. Our results show that the concentration of PLFAs decreased with warming in the subsoil (below 30 cm) by 28 % but was not affected in the topsoil. Phospholipid fatty acid concentrations changed in concert with soil organic carbon. The microbial community response to warming was depth dependent. The relative abundance of Actinobacteria increased in warmed subsoil, and Gram+ bacteria in subsoils adapted their cell membrane structure to warming-induced stress, as indicated by the ratio of anteiso to iso branched PLFAs. Our results show for the first time that subsoil microorganisms can be more affected by warming compared to topsoil microorganisms. These microbial responses could be explained by the observed decrease in subsoil organic carbon concentrations in the warmed plots. A decrease in microbial abundance in warmed subsoils might reduce the magnitude of the respiration response over time. The shift in the subsoil microbial community towards more Actinobacteria might disproportionately enhance the degradation of previously stable subsoil carbon, as this group is able to metabolize complex carbon sources.

54 ENVIRONMENTAL SCIENCES↗

Sustainable Aviation Fuel from High-Strength Wastewater via Membrane-Assisted Volatile Fatty Acid Production: Experimental Evaluation, Techno-economic, and Life-Cycle Analyses

To reduce emissions from combustion of fossil fuels, sustainable aviation fuels (SAFs) have the potential to decarbonize the aviation sector. Redirecting wastes from conventional waste management practices and using them as cost-effective feedstocks for low-carbon fuels can reduce emissions from both waste disposal and fuel combustion. One approach is to upgrade wet wastes to SAF precursors, such as volatile fatty acids (VFAs). Here, in this study, novel membrane-assisted arrested methanogenesis was developed to convert high-strength wastewater to VFAs. Based on experimental results of VFA production, techno-economic and life-cycle analyses were conducted to estimate the potential economic and environmental benefits of SAF production from high-strength wastewater via VFAs. By evaluating three proposed scenarios for VFA production, a minimum production cost of VFA is achieved at $\$$0.60/kg VFA at a wastewater flow rate of 1100 MT/d. For the corresponding VFA-derived SAF, the estimated minimum fuel selling price is $\$$4.64/gasoline gallon equivalent. The life-cycle analysis shows that up to a 71% reduction in greenhouse gas emissions can be achieved relative to its fossil-counterpart along with lower water and fossil-fuel consumption.

09 BIOMASS FUELS↗

PDMS ‐silica composite gas separation membranes by direct ink writing

Abstract Polydimethylsiloxane (PDMS)‐based membranes containing amine‐functionalized and unfunctionalized silica particles were fabricated via direct ink writing for CO 2 /N 2 gas separation. The printability of the inks was evaluated by rheological measurements, while spectroscopy, microscopy, thermal measurements, and mechanical testing were employed to characterize the printed membranes. The surface morphology of the membranes revealed the absence of voids, demonstrating their suitability for gas separation. The printed membranes also exhibited desirable thermal and mechanical properties (i.e., thermal degradation temperature of 518 °C and tensile strength as high as 1.178 MPa with 529% elongation). The PDMS‐based membranes generally displayed high permeability for CO 2 but slightly low selectivity for the CO 2 /N 2 gas pair. The best‐combined permeability‐selectivity performance of 8794 barrer and selectivity of 11.64 was demonstrated by the printed PDMS membrane containing no SiO 2 fillers. The inclusion of unfunctionalized SiO 2 particles generally increased the membrane's gas permeability but compromised the selectivity. In contrast, membranes with amine‐functionalized silica showed improved selectivity compared to membranes containing unfunctionalized silica. Overall, the performance and characteristics offered by the PDMS/silica composite membranes demonstrated the potential of 3D printing as an economical and sustainable fabrication approach to developing materials for carbon capture applications.

Gutierrez, Dianne B.↗

Pectin methylesterase selectively softens the onion epidermal wall yet reduces acid-induced creep

De-esterification of homogalacturonan (HG) is thought to stiffen pectin gels and primary cell walls by increasing calcium cross-linking between HG chains. Contrary to this idea, recent studies found that HG de-esterification correlated with reduced stiffness of living tissues, measured by surface indentation. The physical basis of such apparent wall softening is unclear, but possibly involves complex biological responses to HG modification. To assess the direct physical consequences of HG de-esterification on wall mechanics without such complications, we treated isolated onion (Allium cepa) epidermal walls with pectin methylesterase (PME) and assessed wall biomechanics with indentation and tensile tests. In nanoindentation assays, PME action softened the wall (reduced the indentation modulus). In tensile force/extension assays, PME increased plasticity, but not elasticity. These softening effects are attributed, at least in part, to increased electrostatic repulsion and swelling of the wall after PME treatment. Despite softening and swelling upon HG de-esterification, PME treatment alone failed to induce cell wall creep. Instead, acid-induced creep, mediated by endogenous α-expansin, was reduced. We conclude that HG de-esterification physically softens the onion wall, yet reduces expansin-mediated wall extensibility.

59 BASIC BIOLOGICAL SCIENCES↗

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗

Electrochemical Evolution of Fuel Cell Platinum Nanocatalysts on Carbon Nanotubes at the Atomic Scale

The evolution of Pt nanoparticles supported on carbon nanotubes is analyzed before and after electrochemical potential cycling, using identical location aberration-corrected transmission electron microscopy, for applications in proton exchange membrane fuel cells. The work is focused on the half-cell accelerated stress test protocol of potential cycles ranging between 1.0 and 1.5 V RHE to represent the start-up/shutdown settings of a fuel cell vehicle. The research work reveals that particle migration and coalescence are key mechanisms for a reduction in the Pt nanoparticle surface area at the early stages of potential cycling. Further, the mechanism for particle movement and coalescence is attributed to carbon corrosion, catalyzed either by Pt or by bulk corrosion of the carbon nanotubes. Carbon corrosion results in the appearance of carbon vacancies at the carbon nanotube/Pt nanoparticle interface during cycling, as well as the formation of edge and surface defects. During cycling, the concentration of the dissoluble Pt increases. As soon as a significant amount is reached, subnanometer/atomic clusters emerge on the carbon nanotube support, which can move and coalesce, or redeposit on the surface of larger particles through Ostwald ripening.

25 ENERGY STORAGE↗

Solid State Air Purification System

Life support systems in spacecraft are designed to provide a safe, habitable environment for the astronauts, and one of the most significant challenges is managing acceptable air quality. Carbon dioxide (CO2) is respired normally by humans at concentrations that are toxic if inhaled directly, and as a result cabin air must be tightly managed. The Carbon Dioxide Removal Assembly (CDRA) currently on board the ISS is the best functioning technology for manned space cabins, but has two significant drawbacks:1. The CDRA requires that air be dried prior to CO2 capture, and this costs energy _ in fact, the system spends 4X more energy drying the air than in actually capturing and releasing carbon dioxide. 2. The CDRA works in batch mode, while downstream CO2 processing systems require a continuous stream of CO2. This adds unnecessary complexity, as well as a second parasitic energy loss.An ideal system would process CO2 continuously without any need for drying of the air, and without any moving parts. Such a system would require a fraction of the size and weight of the CDRA while dropping the cost of CO2 capture by 5X or more. Such a technology would be enabling for future long term manned flight missions, such as a mission to Mars. eSionic is developing a new electrochemical membrane technology using its patented innovations in electrolyte materials. In Phase I of this program eSionic has demonstrated continuous gas separation using only electricity to drive the separation, with no moving parts or pressure drops. In Phase II, eSionic will demonstrate long-term operation of the membranes consistent with the needs of NASA for this development program.

Life Support↗

High Performance PEFC Electrode Structures

Raytheon Technologies Research Center (RTRC) in collaboration with Ion Power Inc. and the University of Arkansas at Little Rock and the FC-PAD consortium executed a project that: (1) developed comprehensive models of oxygen and proton transport in cathode catalyst layers that provided new insights about losses associated with reducing platinum loading to 0.1 mg/cm 2 , (2) designed, fabricated, characterized, and tested cells featuring carbon-supported catalyst layers with low platinum loadings that met efficiency and power density targets set forth by the Hydrogen and Fuel Cells Technology Office, and (3) designed, fabricated, characterized, and tested novel catalyst structures. The modeling efforts produced eight scientific publications that shared new descriptions of oxygen and proton transport in catalyst layers with the broader technical community. The key physical insights from the models are expressed in straightforward algebraic expressions, facilitating easy adoption by other researchers. The models developed during the project explain why resistance to oxygen transport is inversely proportional to interfacial area of platinum – an observation that eluded quantitative explanation for a decade. The models quantitatively predict polarization when measured morphological parameters and transport properties are input. Membrane-electrode assemblies made during the project met stated goals for current at high voltage and power density at rated voltage for transportation fuel cells at the end of budget period 2. High performance was achieved by developing a diffusion layer with low resistance to oxygen transport and a PtCo/C cathode catalyst layer capable of supporting rapid proton and oxygen transport. The project was subsequently directed to curtail experimental work and focus on modeling during budget period 3. Ion Power Inc. developed new expertise in fabricating catalyst layers containing platinum-cobalt catalysts, and processing very thin membranes. The University of Arkansas at Little Rock developed novel nanocolumnar self-supported thin film electrocatalysts that can be grown on carbon supports using a simple high pressure sputter deposition method. The nanocolumnar microstructure provides adequate surface-to-volume ratio for efficient platinum utilization, and the conformal platinum shell with larger crystal grain sizes covering the carbon support surface may eliminate durability issues associated with catalyst dissolution, agglomeration, and carbon corrosion.

08 HYDROGEN↗

Controlled Acidity Gradients Enable CO 2 Reduction to Formic Acid (Not Formate) by Molecular Electrocatalysts

Neutral or basic conditions are commonly required for the selective electrochemical reduction of CO 2 , leading to the accumulation of carbonate salts and the generation of formate rather than formic acid. A generalizable strategy for obtaining formic acid (not formate) in the electroreduction of CO 2 with molecular catalysts is introduced, based on controlling acidity gradients using a dual-electrolyte cell with a proton-exchange membrane. This approach uses anodic water oxidation as the source of protons and electrons for CO 2 reduction to formic acid, while mitigating H 2 evolution near the cathode and avoiding carbonate formation. Mechanistic studies, including systems modeling, provide insight into the origin of the formic acid selectivity and guide the broader implementation of this strategy in molecular electrocatalysis for CO 2 utilization.

Alcohols↗