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Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗

Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst for enhanced CO 2 -methanol conversion at low temperature and pressure

Cu-ZnO-Al 2 O 3 is the most widely applied catalyst for CO 2 hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al 2 O 3 nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h –1 kg –1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements under the 1 bar reveal that the CO 2 hydrogenation to methanol on the ZnO nanoarray supported Cu-ZnO-Al 2 O 3 catalyst follows the CO reaction pathway, due to the surface oxygen vacancies on ZnO nanorods which facilitate CO 2 dissociation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Topology optimization of additively manufactured fluidic components free of internal support structures

This report integrates projection-based approaches for implementing overhang constraints with fluid topology optimization to design additively manufactured fluidic components that do not require internal support structures. Internal support structures are challenging, potentially impossible to remove in complex fluid networks, yet would degrade fluidic performance if left within the part. This presents a major challenge in coupling topology optimization with additive manufacturing in the design of fluid components. The proposed approach leverages past work in overhang constraints for solid mechanics, including projection formulations and adjoint sensitivity analysis, and considers incompressible Navier–Stokes equations for laminar fluid flow. The approach is demonstrated on 2D and 3D fluid topology optimization problems to minimize pressure drop and constrain mass flow rates in pipes and manifolds. Resulting designs are crisp, logical, satisfy performance constraints, and satisfy overhang constraints, eliminating the need for internal support structures.

42 ENGINEERING↗

Effect of Si/Al ratio of ZSM-5 support on structure and activity of Mo species in methane dehydroaromatization

The effect of the Si/Al ratio of the ZSM-5 support on the structure and activity of Mo/HZSM-5 catalysts in methane dehydroaromatization (MDA) was studied. ZSM-5 (with Si/Al = 15, 25, and 40) supported Mo oxide catalysts (MoOx/ZSM-5) with 3 and 10 wt% Mo loading were prepared by incipient wetness impregnation followed by calcination in air at 500 °C. The as-prepared catalysts were activated by temperature programmed reduction in hydrogen in order to maximize Mo dispersion. To understand the structure-activity relationship, the fresh and spent samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption isotherms, Scanning Transmission Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (STEM-EDS), X-ray absorption spectroscopy (EXAFS and XANES), thermogravimetric analysis (TGA), and Raman spectroscopy. The results show that the Si/Al ratio does not influence the the local structure around the Mo centers. It does however affect the number of available Brønsted acid sites in the support and the amount of Mo species entering the zeolite channels. A lower Si/Al ratio and higher Mo loading resulted in a higher Mo occupation within the zeolite channels. The higher channel occupation directly correlated with higher benzene selectivity and yield, as well as a lower catalyst deactivation rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Progress in metal-supported solid oxide electrolysis cells: A review

There is increasing global interest in using solid oxide electrochemical cells to perform electrolysis. Metal-supported solid oxide electrolysis cells (MS-SOEC) are being developed with stainless steel and Ni-based supports. Additionally, the use of porous metal to support the electrochemically-active layers is anticipated to improve mechanical strength, decrease cost, and increase tolerance to aggressive operating conditions, including rapid thermal excursions. This review summarizes and analyzes the previous decade of progress in MS-SOEC development, and identifies critical needs for future work.

08 HYDROGEN↗

Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

aqueous phase reactions↗

Progress in durability of metal-supported solid oxide fuel cells with infiltrated electrodes

High power density and longevity are required to commercialize solid oxide fuel cells for vehicular applications. In this work, electrochemical durability of high-performance metal-supported solid oxide fuel cells (MS-SOFCs) with infiltrated catalysts is investigated. Durability screening of various cathode and anode compositions is conducted. The Pr 6 O 11 cathode and SDCN 40 (40 vol% Ni-60 vol% SDC) anode are selected due to preferential tradeoff between performance and durability. X-ray diffraction indicates the catalyst phases are stable after prolonged thermal annealing. Electrochemical impedance and scanning electron microscopy analyses show that the evolution of SDCN40 is minimal, and coarsening and Cr poisoning of the Pr 6 O 11 catalyst are the dominant degradation mechanisms. These degradation mechanisms are addressed by implementing three additional fabrication steps: (1) preoxidation of the metal support, (2) deposition of thin and protective atomic layer deposition (ALD) coatings throughout the cathode-side electrode and support, and (3) in situ pre-coarsening of the catalysts. A favorable tradeoff is achieved: the combination of the three fabrication steps reduces degradation rate at 0.7 V and 700 °C by two orders of magnitude to 2.3% kh -1 , while sacrificing 35% of initial power density. The catalyst pre-coarsening step is primarily responsible for the loss of performance.

25 ENERGY STORAGE↗

Long term durability test and post mortem for metal-supported solid oxide electrolysis cells

Hydrogen is a renewable energy carrier, and electrolysis to split water is the most environmentally friendly method to produce hydrogen. This work reports long-term durability and degradation mode analysis for metal-supported solid oxide electrolysis cells (MS-SOECs). Catalyst screening showed that MS-SOECs with composite electrode catalysts (samarium-doped ceria-nickel [SDC-Ni] serving as a fuel electrode catalyst, and praseodymium oxide [PrO x ]-SDC or La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 [LSCF]-SDC serving as an air electrode catalyst) exhibit the highest electrochemical performance at 700 °C. The degradation rate of cells with LSCF-SDC as the air electrode catalyst was as low as 1.3%/100 h in long term durability tests at a current density of 0.33 A cm -2 , in contrast to rapid degradation observed for a cell with a PrO x -SDC air electrode. Furthermore, post-mortem analysis reveals the degradation is dependent on the primary modes of fuel electrode catalyst coarsening and Cr poisoning on the air electrode catalyst, as well as secondary modes of oxidation of the metal support and local elemental accumulation of Ni. Other degradation modes reported in conventional anode-supported SOECs, such as Ni migration, foreign element contamination, delamination of the cell, and nano-voids on the electrolyte, are not observed in the present MS-SOECs.

25 ENERGY STORAGE↗

Support size regulated ruthenium-sulfoacid-nitrogen sites intensify cellulose hydrogenolysis to 1,2-propylene glycol

Rational design of metal-acid-base multifunctional catalysts for upgrading cellulose to 1,2-propylene glycol (1,2-PG) is of great significance for building a sustainable world. However, it is time-consuming and tedious to regulate metal-acid-base sites to balance major reactions to render a high 1,2-PG yield. We herein report support size simultaneously regulated ruthenium-sulfoacid-nitrogen (Ru–SO 3 H–N) sites for cellulose hydrogenolysis to high yield 1,2-PG. Originated from the depolymerization and reassembly of zinc-1,3,5-benzenetricarboxylic acid (ZnBTC) fiber with zeolitic imidazolate framework (ZIF-8) in water, 2-methylimidazole infiltrated nanorod (ZnBTC(mIM)) with a varied aspect ratio was fabricated by varying the feed ratio of ZIF-8/ZnBTC. Upon being pyrolyzed, sulfonated and impregnated with Ru ions, the supported sites were tailored in terms of Ru single-atom/nanocluster ratio, SO 3 H acidity and N basicity. Further, the elaborately fabricated catalyst delivers 32.3% yield of 1,2-PG, corresponding to a high productivity of 67.71 mol h -1 g Ru -1 and a large turnover number of 34193, two and three orders of magnitude higher than those by using other Ru-containing catalytic systems for cellulose hydrogenolysis. The excellent performance can be attributed to optimized electronic and molecular structure of Ru–SO 3 H–N sites that can improve rate-determining cellulose hydrolysis/fructose hydrogenolysis, pivotal glucose isomerization with others to proceed at a matched rate. This study opens a new avenue to facilely tailor the metal-acid-base sites by rational design of size controlled supporting matrix.

1,2-Propylene glycol↗

Cooperative roles of water and metal-support interfaces in the selective hydrogenation of cinnamaldehyde over cobalt boride catalysts

Chemoselectivity in the hydrogenation of carbonyl over alkene bonds is valuable for producing industrial chemicals. In this study, we investigate the role of water in the selective hydrogenation of cinnamaldehyde on cobalt and cobalt boride catalysts by combining rate measurements, in situ characterization, and computational calculations. Ex situ and in situ spectroscopic analyses indicate that the boron species do not significantly modify the intrinsic electronic properties of cobalt. However, during thermal treatments, they exsolve from the bulk phase and become enriched on the surface, forming acidic species that enhance the activity and selectivity of carbonyl bond hydrogenation by three and two times, respectively. A small amount of water is able to promote hydrogenation. When titania, ceria, and zirconia are used as supports, metal-support interactions result in smaller particles that show a drop in selectivity toward the desirable unsaturated alcohol. Overall, the combination of the presence of boron species and strong metal-support interactions protects the catalysts from water attack, resulting in enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction and Agglomeration of Supported Metal Clusters Induced by High-Flux X-ray Absorption Spectroscopy Measurements

Supported metal clusters are widely used in catalysis for many important reactions. To understand the catalytic properties, in situ/operando characterization techniques, such as X-ray absorption spectroscopy (XAS), provide essential details of the size, shape, and chemical composition of the cluster and the nature of the active sites. New-generation synchrotrons combined with focusing beamlines provide high-flux-density X-rays for improved detection sensitivity as well as higher time and spatial resolution. Understanding the effects of a high-flux-density X-ray beam on the catalyst during the actual measurement, whether XAS or another synchrotron-based technique, is crucial. This is especially important for in situ and operando studies where both the high flux density and reaction conditions can affect the catalyst structure. In this work, we investigated the effect of the flux density on rhodium clusters supported on Al 2 O 3 at two different beamlines: National Synchrotron Light Source II beamline 08-ID and Stanford Synchrotron Radiation Light Source (SSRL) beamline 4-1. We show that the higher flux density at beamline 08-ID causes the reduction of the highly dispersed RhO x /Al 2 O 3 catalyst, even at room temperature. Additionally, exposure to the higher flux density X-rays at beamline 08-ID during in situ reduction results in significant agglomeration of the Rh clusters. The final size of the Rh nanoparticles reduced at 310 °C is equivalent to that of particles formed after the reduction at 600–650 °C in the absence of the beam. Significant beam-induced reduction and agglomeration is also shown for Ni supported on beta zeolite during in situ reduction at an intermediate-flux-density beamline 9-3 at SSRL, indicating that beam-induced changes in heterogeneous catalysts could be common at intermediate- and high-flux-density beamlines. We provide precautions and recommendations for detecting and minimizing beam damage during in situ/operando XAS measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nitrogen-Doped PtNi Catalysts on Polybenzimidazole-Functionalized Carbon Support for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells

PtM (M = 3d transition metals) alloys are known as the promising oxygen reduction reaction catalysts and have been considered as the replacement of pure Pt catalysts for the commercialization of proton exchange membrane fuel cells. Although great progress has been made in the past three decades, the performance and durability of PtM catalysts still face stringent challenges from practical applications. Functionalization of a catalyst carbon support with nitrogen-contained groups can add charges onto its surface, which can be utilized to build a more complete ionomer/catalyst interface, to reduce the catalyst particle size, and to improve particle size distribution. Nitriding of PtNi catalysts can effectively improve the catalyst activity and stability by the modification of lattice strain. Hereby, we propose a synergistic approach of combining polybenzimidazole-grafted Vulcan XC72 carbon as the catalyst carbon support and the nitriding of PtNi to develop PtNiN/XC72-polybenzimidazole catalysts. Such PtNiN/XC72-PBI catalysts exhibit the excellent performance of fuel cell membrane electrode assembly (i.e., mass activity, 440 mA mgPt –1 ; electrochemical surface area, 51 m 2 gPt –1 ; and rated power density, 836 mW cm –2 ) as well as promising catalyst stability. The developed PtNiN/XC72-PBI meets the US DOE 2020 targets of mass activity for the fuel cell catalysts. This work provides a novel approach and a promising pathway on the development of the catalyst using such a synergistic approach-modification of the catalyst structure by nitrogen doping and functionalization of carbon support by polybenzimidazole for both high performance and high durability.

25 ENERGY STORAGE↗

Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization

Metal–organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr 6 ) offer new opportunities as supports for catalysts with well-defined, essentially molecular, structures. We used the precursor Rh(C 2 H 4 ) 2 (acac) (acac is acetylacetonate) to anchor Rh(I) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization in a once-through flow reactor at 298 K and 1 bar. The catalyst performance data are complemented with structural information determined by infrared and extended X-ray absorption fine structure spectroscopies and by calculations at the level of density functional theory, the latter carried out also to extend the investigation to a related MOF, NU-1000. The agreement between the experimental and calculated structural metrics is good, and the calculations have led to predictions of reaction mechanisms and associated energetics. Finally, the data demonstrate a correlation between the catalytic activity and selectivity and the electron-donor tendency of the supported rhodium (as measured by the frequencies of CO ligands bonded as probes to the Rh(I) centers), which is itself a measure of the electron-donor tendency of the support.

36 MATERIALS SCIENCE↗

Supported Oxygen Evolution Catalysts by Design: Toward Lower Precious Metal Loading and Improved Conductivity in Proton Exchange Membrane Water Electrolyzers

Reducing the precious metal content of water oxidation catalysts for proton-exchange-membrane water electrolyzers remains a critical barrier to their large-scale deployment. Herein, we present an engineered architecture for supported iridium catalysts, which enables decreased precious metal content and improved activity and conductivity. The improvement in performance at lower precious metal loading is realized by the deposition of a conformal layer of platinum nanoparticles on titanium dioxide (TiO 2 ) using a facile photoreduction method to prepare conductive layer coated supports (CCSs). Platinum nanoparticles are homogeneously dispersed on TiO 2 , and the conductivity of the subsequent catalysts with 39 wt % precious group metal loadings is significantly higher than the commercial 75 wt % loaded IrO 2 -TiO 2 catalysts. The conformal conductive layer also maintains an enhanced conductivity and electrochemical activity upon thermal annealing when compared to catalysts without the conductive layer and nonconformal heterogeneous conductive layer. The iridium mass activity from half-cell studies shows a 141% improvement for CCS supported catalysts at 42% lower loadings compared to the commercial catalysts. The conductive layer also improves the single cell electrolyzer performance at a similar catalyst loading in comparison to a commercial state-of-the-art catalyst. Here, we correlate the physical properties of the engineered catalysts with their electrochemical performance in electrolyzers to understand structure-activity relationships, and we anticipate further performance improvements upon synthesis and materials optimizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 Methanation on Cu-Cluster Decorated Zirconia Supports with Different Morphology: A Combined Experimental In Situ GIXANES/GISAXS, Ex Situ XPS and Theoretical DFT Study

We report that subnanometer copper tetramer-zirconia catalysts turn out to be highly efficient for CO 2 hydrogenation and its conversion to methane. The cluster size and substrate morphology are controlled to optimize the catalytic performance. The two types of zirconia supports investigated are prepared by atomic layer deposition (~ 3 nm thick film) and supersonic cluster beam deposition (nanostructured film, ~ 100 nm thick). The substrate plays a crucial role in determining the activity of the catalyst as well as its cyclability over repeated thermal ramps. A temperature-programmed reaction combined with in situ X-ray characterization reveals the correlation between the evolution in the oxidation state and catalytic activity. Ex situ photoelectron spectroscopy indicates Cu clusters with stronger interactions with the nanostructured film, which can be the cause for the higher activity of this catalyst. Density functional theory calculations based on the Cu 4 O 2 cluster supported on a ZrOx subunit reveal low activation barriers and provide mechanism for CO 2 hydrogenation and its conversion to methane. Altogether, the results show a new way to tune the catalytic activity of CO 2 hydrogenation catalysts through controlling the morphology of the support at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Oxidation of Methane to Methanol Enabled by Electronic Atomic Monolayer–Metal Support Interaction

Direct, catalytic oxidation of methane to methanol (MTM) with molecular oxygen is a highly desirable process to valorize methane. We propose that Rh-doped graphene (GR) supported on Ni(111) can be a promising catalyst for MTM with appreciable activity and selectivity. In the absence of the Ni(111) support, a MTM process is difficult. The catalytic activity of the Rh-doped GR is enabled by the Ni(111) support that covalently binds the Rh-doped GR and significantly modifies its properties, leading to facile O 2 activation by the synergy of the Rh dopant and the neighboring carbon atom of GR. The highly activated O 2 and the Rh dopant in turn activate CH 4 . Strikingly, the methane C–H bond breaking is preferred over methanol C–H bond breaking at 473 K. Here, the strong interaction between TM-doped GR and Ni(111) is found to be a general mechanism for regulating the adsorption strength of various molecules, providing important insight for tuning the properties of single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fischer–Tropsch Synthesis at a Low Pressure on Subnanometer Cobalt Oxide Clusters: The Effect of Cluster Size and Support on Activity and Selectivity

In this study, the catalytic activity and changes in the oxidation state during the Fischer Tropsch (FT) reaction was investigated on subnanometer size-selected cobalt clusters deposited on oxide (Al2O3, MgO) and carbon-based (ultrananocrystalline diamond UNCD) supports by temperature programmed reaction (TPRx) combined with in-situ grazing-incidence X-ray absorption characterization (GIXAS). The activity and selectivity of ultrasmall cobalt clusters exhibits a very strong dependence on cluster size and support. The evolution of the oxidation state of metal cluster during the reaction reveals that metal-support interaction plays a key role in the reaction.

Fischer - Tropsch reaction↗

Energy, power, and infrastructure demands from electrifying airport ground support equipment at United States airports

As the airline industry seeks to reduce costs and transition to clean energy, electric ground support equipment is emerging as a favorable option. The integration of electric ground support equipment into airport operations requires careful planning for vehicle deployment, charging infrastructure, and grid impacts. We develop a flexible, bottom-up modeling framework to assess energy and infrastructure needs across more than 300 U.S. airports. Our analysis estimates site-specific power and energy demand, equipment counts by type, charger requirements, and costs. Here we quantify the magnitude of new electrical loads created by the electrification of airport ground support equipment, finding that peak power demand at the largest airports can reach up to 20 megawatts, with annual electricity consumption approaching 51,000 megawatt-hours. We further show that behind-the-meter battery energy storage systems and solar photovoltaic systems can reduce peak load and lower total system costs by as much as 10 million dollars.

24 POWER TRANSMISSION AND DISTRIBUTION↗