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Biospheric feedback effects in a synchronously coupled model of human and Earth systems

Fossil fuel combustion and land-use change are the first and second largest contributors to industrial-era increases in atmospheric carbon dioxide concentration, which is itself the largest driver of present-day climate change1. Projections of fossil fuel consumption and land-use change are thus fundamental inputs for coupled Earth system models (ESM) used to estimate the physical and biological consequences of future climate system forcing2,3. While empirical datasets are available to inform historical analyses4,5, assessments of future climate change have relied on projections of energy and land use based on energy economic models, constrained using historical and present-day data and forced with assumptions about future policy, land-use patterns, and socio-economic development trajectories6. Here we show that the influence of biospheric change – the integrated effect of climatic, ecological, and geochemical processes – on land ecosystems has a significant impact on energy, agriculture, and land-use projections for the 21st century. Such feedbacks have been ignored in previous ESM studies of future climate. We find that synchronous exposure of land ecosystem productivity in the economic system to biospheric change as it develops in an ESM results in a 10% reduction of land area used for crop cultivation; increased managed forest area and land carbon; a 15-20% decrease in global crop price; and a 17% reduction in fossil fuel emissions for a low-mid range forcing scenario7. These simulation results demonstrate that biospheric change can significantly alter primary human system forcings to the climate system. This synchronous two-way coupling approach removes inconsistencies in description of climate change between human and biosphere components of the coupled model, mitigating a major source of uncertainty identified in assessments of future climate projections8-10.

climate change↗

Design and Implementation of Geothermal Energy Systems at West Chester University

West Chester University has launched a comprehensive transformation of its campus heating and cooling systems from traditional fossil fuels to geothermal. This change will significantly decrease the institution's carbon footprint and serve as a national model for green campus efforts. The institution has designed a phased series of projects to build a district geo-exchange system with shared well fields, central pumping station and distribution piping to provide the geo-exchange water to campus buildings as their internal building HVAC systems are changed to be able to use the geo-exchange water. This project addresses the US Department of Energy Office of Energy Efficiency and Renewable Energy (EERE) goal to invest in clean energy technologies that strengthen the economy, protect the environment, and reduce dependence on foreign oil. In addition, this project advances EERE's efforts to establish geothermal energy as an economically competitive contributor to the US energy supply.

15 GEOTHERMAL ENERGY↗

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

The abundance of inexpensive, natural gas has transformed the energy landscape, whereby revealing new possibilities for sustainable chemical technologies or impacting those that have relied on traditional fossil fuels. The primary component, methane, is underutilized and wastefully exhausted, leading to anthropogenic global warming. Historically, the manipulation of methane remained “ clavis aurea ,” an insurmountable yet rewarding challenge and thus the focus of intense research. This is primarily due to an inability to dissociate C–H bonds in methane selectively, which requires a high energy penalty and is an essential prerequisite for the direct conversion of methane into a large set of value-added products. The discovery of such processes would promise an energy gainful use of natural gas benefiting several essential chemical processes associated with C1 chemistry. This first C–H bond dissociation step of the methane molecule appears in numerous catalytic mechanisms as the rate-determining step or most essential barrier sequence for all subsequent steps that follow in the production of C–C, C–O, or C x –H y –O z bonds found in value added products. A main goal is to catalytically reduce the energy barrier for the first C–H bond dissociation to be able to achieve the activation of methane at low or moderate temperatures. As such there is great value in understanding the fundamental nature of the active sites responsible for bond breaking or formation and thus be able to facilitate better control of this chemistry, leading to the development of new technologies for fuel production and chemical conversion. Surface science studies offer enhanced perspectives for a careful manipulation of bonds over the last layer atoms of catalyst surfaces, an essential factor for the design of atomically precise catalysts and unravelling of the reaction mechanism. With the advent of new surface imaging, spectroscopy, and in situ tools, it has been possible to decipher the surface chemistry of complex materials systems and further our understanding of atomic active sites on the surfaces of metals, oxides, and carbides or metal–oxide and metal–carbide interfaces. The once considered near impossible step of C–H bond activation is now observed at low temperatures with high propensity over a collection of oxide, metal–oxide, and metal–carbide systems in a conventional or inverse configuration (oxide or carbide on metal). The enabling of C–H activation at low temperature has opened interesting possibilities for the specific production of chemicals such as methanol directly from methane, a step toward facile synthesis of liquid fuels. We highlight the most recent of these results and present the key aspects of active site configurations engineered from surface science studies which enable such a simple reactive event through careful manipulation of the last surface layer of atoms found in the catalyst structure. New concepts which help in the activation and conversion of methane are discussed.

36 MATERIALS SCIENCE↗

Assessment of Technoeconomic Opportunities in Automation for Nuclear Microreactors

Achieving full decarbonization of all economic sectors remains a challenge, especially in niche markets. For example, remote communities and industrial or mining activities detached from the main electric grid heavily rely on fossil fuels, similar to urban and industrial microgrids with combined heat and power needs. A combination of renewables and energy storage is often not suitable due to cost, reliability, intermittency, and large storage requirements. Small nuclear reactors with a flexible purpose could serve these applications. Microreactors (MR) are a class of reactors that are compact, factory manufactured, transportable, and self-regulating. Typically, they generate much less power than their large reactor counterparts. The main advantages of microreactors include the versatile nature of the energy produced, the reliability of supply, and freedom from having to transport and store large quantities of fuels on-site, coupled with the absence of dependence on an electrical grid. A strong business case is needed to move from the microreactor prototype to the commercialization phase. In fact, fossil fuels are still relatively inexpensive, and in the near term, carbon credits will be available to virtually compensate for emissions. For microreactors, one of the main costs in operation and maintenance (O&M) is their staffing levels. In this study, we investigate how to optimize the number (and thus the cost) of workers, moving from a traditional, fully manned, on-site personnel approach to an unmanned, remote personnel approach. We examine four different staffing models that can be implemented as the technology matures and evolves. We estimate the staffing needs of each model and build a business case to justify the substitution of on-site personnel with adequate technologies. To do so, we propose a cost model to quantify potential cost reductions from automating O&M activities. The model accounts for both the reduction in cost derived from the reduced number of full-time-equivalent (FTE) employees and the increase in cost derived from the need to buy new control hardware as needed. Applying the cost model that we created to different scenarios, an on-site O&M cost reduction exceeding 80% can be expected. Additionally, we found that it is more impactful to focus on automating routine O&M tasks rather than attempting to automate transient management (shutdowns, restarts, monitoring condition deviations). In fact, transients typically account for less than 1% of the total FTE time spent on the reactors.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Design and Implementation of Geothermal Energy Systems at West Chester University

West Chester University has launched a comprehensive transformation of its campus heating and cooling systems from traditional fossil fuels (coal, oil and natural gas) to geothermal. This change will significantly decrease the institution’s carbon footprint and serve as a national model for green campus efforts. The institution has designed a phased series of projects to build a district geo-exchange system with shared well fields, central pumping station and distribution piping to provide the geo-exchange water to campus buildings as their internal building HVAC systems is changed to be able to use the geo-exchange water. This project addresses the US Department of Energy Office of Energy Efficiency and Renewable Energy (EERE) goal to invest in clean energy technologies that strengthen the economy, protect the environment, and reduce dependence on foreign oil. In addition, this project advances EERE’s efforts to establish geothermal energy as an economically competitive contributor to the US energy supply.

15 GEOTHERMAL ENERGY↗

Impacts of policy and market incentives for solid waste recycling in Dhaka, Bangladesh

Highlights: • Bangladesh’s industry and population are growing rapidly, producing more urban waste. • Recycling reduces the solid waste management burden of Municipalities. • A wide array of informal and formal actors is involved in collection and recycling. • Demand for recycled materials and renewable energy creates market incentives. • Policy incentives exist, but they only reach the formal industry. - Abstract: Solid waste mismanagement in Dhaka, Bangladesh, illustrates a well-known market failure which can be summarized as: waste is a resource in the wrong place. Inorganic materials such as plastic or paper can be used to feed the demand for recycled materials in the industrial sector. Organic materials can be converted and used in the nutrient-starved agricultural sector which is currently heavily depending on chemical fertilizers. They are also a feedstock to generate renewable energy in the form of biogas for this energy-starved country relying on diminishing natural gas reserves and increasing import of coal. Reality however does not capitalize on this potential; instead the waste is a burden for municipal authorities who spend large portions of their budgets attempting to transport it out of the city for discharge into landfills. The major part of these materials still remains uncollected in the residential areas and is discarded indiscriminately in open spaces, polluting the residents’ living environment including water, soil and air resources, in the city and beyond. Bangladeshi authorities have, to some extent, recognized this market failure and have developed policies to encourage the development of waste recycling activities. It is also important to note that this market failure is only partial: a large, mostly informal recycling sector has developed in Bangladesh, focusing on inorganic recyclables of market value. The fact that this sector remains largely informal means that these actors perceive significant barriers to formalization. Comparatively, the organic waste recycling sector is less driven by market mechanisms. Competition from chemical fertilizers and fossil fuels is fierce and hinders the development of market opportunities for compost and renewable energy. Nevertheless commercial production of compost and biogas from organic municipal waste is formalized and benefiting from policy incentives.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Wireless microwave acoustic sensor system for condition monitoring in power plant environments

This project successfully demonstrated novel wireless microwave acoustic temperature and pressure sensors that can be embedded into equipment and structures located in fossil fuel power plant environments to monitor the condition of components such as steam headers, re-heat lines, water walls, burner tubes, and power turbines. The wireless microwave acoustic sensor technology researched and developed through a collaborative partnership between the University of Maine and Environetix Technologies Corporation can provide a revolutionary impact in the power industry since it is anticipated that the wireless sensors will deliver reliable real-time sensing information in harsh power plant conditions that involve temperatures up to 1100oC and pressures up to 750 psi. The work involved the research and development of novel high temperature harsh environment thin film electrodes, piezoelectric smart microwave acoustic sensing elements, sensor encapsulation materials that were engineered to function over long times up to 1100oC, and a radio-frequency (RF) wireless interrogation electronics unit that are located both inside and outside the high temperature harsh environment. The UMaine / Environetix team have interacted with diverse power plant facilities, and identified as a testbed a local power generation facility, which burns municipal solid waste (MSW), the Penobscot Energy Recovery Company (PERC), Orrington, Maine. In this facility Environetix / UMaine successfully implemented and tested multiple wireless temperature sensor systems within the harsh-environment of the economizer chamber and at the boiler tubes, transferring the developed technology to the power plant environment to perform real-time sensor monitoring experiments under typical operating conditions, as initially targeted in the project. The wireless microwave acoustic sensor technology developed under this project for power plant applications offers several significant advantages including wireless, battery-free, maintenance-free operation, and operation in the harsh-environment of power plant equipment up to about 1100 oC. Their small size and configuration allows flexible sensor placement and embedding of multiple sensor arrays into a variety of components within power systems that can be interrogated by a single RF unit. The outcomes of this project and technological transfer respond to a DOE analysis need, which indicated that if one percent efficiency in coal burning is achieved, an additional 2 gigawatt-hours of energy per year is generated and the resulting coal cost savings is $300 million per year, also accompanied by a reduction of more than 10 million metric tons of CO2 per year emitted into the atmosphere. Therefore, the developed harsh environment wireless microwave acoustic sensor technology and the technological transfer achievements that resulted from the execution of this project have significant impact for power plant equipment and systems and are well-positioned to contribute to the cost reduction in power generation, the increase in power plant efficiency, the improvement in maintenance, the reduction in down-time, and the decrease in environmental pollution. The technology is also in a position to be extended to address other types of high-temperature harsh-environment power plant and energy sector sensing needs.

20 FOSSIL-FUELED POWER PLANTS↗

Techno-Economic Evaluation of Cellulosic Ethanol Production Based on Pilot Biorefinery Data: a Case Study of Sweet Sorghum Bagasse Processed via L+SScF

Replacing fossil fuels with renewable fuels derived from lignocellulosic biomass can contribute to the mitigation of global warming and the economic development of rural communities. This will require lignocellulosic biofuels to become price competitive with fossil fuels. Techno-economic analyses can provide insights into which parts of the biofuel production process need to be optimized to reduce cost or energy use. Here, we used data obtained from a pilot biorefinery to model a commercial-scale biorefinery that processes lignocellulosic biomass to ethanol, with a focus on the minimum ethanol selling price (MESP). The process utilizes a phosphoric acid-catalyzed pre-treatment of sweet sorghum bagasse followed by liquefaction and simultaneous saccharification and co-fermentation (L+SScF) of hexose and pentose sugars by an engineered Escherichia coli strain. After validating a techno-economic model developed with the SuperPro Designer software for the conversion of sugarcane bagasse to ethanol by comparing it to a published Aspen Plus model, six different scenarios were modeled for sweet sorghum bagasse Under the most optimistic scenario, the ethanol can be produced at a cost close to the energy-equivalent price of gasoline. Aside from an increase in the price of gasoline, the gap between ethanol and gasoline prices could also be bridged by either a decrease in the cost of cellulolytic enzymes or development of value-added products from lignin.

Biofuel↗

Advanced defrosting techniques in air source heat pumps: A review of vapor injection, thermal energy storage, and experimental frost accumulation data

Electrification is a critical step for reducing greenhouse gas emissions from heating. Air source heat pumps (ASHPs) are a promising alternative to fossil fuel-based systems due to their high coefficients of performance (COP), dual heating and cooling capability, and lower carbon footprint. However, for ASHPs to achieve widespread adoption, they must operate reliably across all climates, including cold regions. Additionally, defrosting techniques should be energy efficient and minimally disruptive to indoor comfort. Vapor injection (VI) technology can address the high-pressure and high-temperature lift challenges encountered in low ambient conditions. More recently, in addition to enhancing heating performance, VI has also been shown to improve the speed and efficiency of reverse cycle defrosting. Likewise, thermal energy storage (TES) has steadily gained attention for its ability to serve as an auxiliary heat source during both normal operation and defrosting. This review analyzes the benefits and limitations of VI- and TES-assisted defrosting approaches. While both technologies show strong potential individually, no studies to date have explored their combined use in ASHP systems. Additionally, to support continued development of defrosting strategies, both in modeling and experimental work, it is critical to establish frost accumulation data under a range of operating conditions. By compiling the available data from the literature, this paper also highlights the limited availability of such experimental data and the wide variation in frosting and defrosting durations and termination criteria, which are often influenced by system design and test setups.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Atomic/molecular layer deposition for energy storage and conversion

Energy storage and conversion systems, including batteries, supercapacitors, fuel cells, solar cells, and photoelectrochemical water splitting, have played vital roles in the reduction of fossil fuel usage, addressing environmental issues and the development of electric vehicles. The fabrication and surface/interface engineering of electrode materials with refined structures are indispensable for achieving optimal performances for the different energy-related devices. Atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques, the gas-phase thin film deposition processes with self-limiting and saturated surface reactions, have emerged as powerful techniques for surface and interface engineering in energy-related devices due to their exceptional capability of precise thickness control, excellent uniformity and conformity, tunable composition and relatively low deposition temperature. In the past few decades, ALD and MLD have been intensively studied for energy storage and conversion applications with remarkable progress. In this work, we give a comprehensive summary of the development and achievements of ALD and MLD and their applications for energy storage and conversion, including batteries, supercapacitors, fuel cells, solar cells, and photoelectrochemical water splitting. Moreover, the fundamental understanding of the mechanisms involved in different devices will be deeply reviewed. Furthermore, the large-scale potential of ALD and MLD techniques is discussed and predicted. Finally, we will provide insightful perspectives on future directions for new material design by ALD and MLD and untapped opportunities in energy storage and conversion.

25 ENERGY STORAGE↗

Feasibility of Tidal and Ocean Current Energy in False Pass, Aleutian Islands, Alaska final report

The Aleutian Pribilof Islands Association was awarded a U.S. Department of Energy Tribal Energy Program grant (DE-EE0005624) for the Feasibility of Tidal and Ocean Current Energy in False Pass, Aleutian Islands, Alaska (Project). The goal of the Project was to perform a feasibility study to determine if a tidal energy project would be a viable means to generate electricity and heat to meet long-term fossil fuel use reduction goals, specifically to produce at least 30% of the electrical and heating needs of the tribally-owned buildings in False Pass. The Project Team included the Aleut Region organizations comprised of the Aleutian Pribilof Island Association (APIA), and Aleutian Pribilof Island Community Development Association (APICDA); the University of Alaska Anchorage, ORPC Alaska a wholly-owned subsidiary of Ocean Renewable Power Company (ORPC), City of False Pass, Benthic GeoScience, and the National Renewable Energy Laboratory (NREL). The following Project objectives were completed: collected existing bathymetric, tidal, and ocean current data to develop a basic model of current circulation at False Pass, measured current velocities at two sites for a full lunar cycle to establish the viability of the current resource, collected data on transmission infrastructure, electrical loads, and electrical generation at False Pass, performed economic analysis based on current costs of energy and amount of energy anticipated from and costs associated with the tidal energy project conceptual design and scoped environmental issues. Utilizing circulation modeling, the Project Team identified two target sites with strong potential for robust tidal energy resources in Isanotski Strait and another nearer the City of False Pass. In addition, the Project Team completed a survey of the electrical infrastructure, which identified likely sites of interconnection and clarified required transmission distances from the tidal energy resources. Based on resource and electrical data, the Project Team developed a conceptual tidal energy project design utilizing ORPC’s TidGen® Power System. While the Project Team has not committed to ORPC technology for future development of a False Pass project, this conceptual design was critical to informing the Project’s economic analysis. The results showed that power from a tidal energy project could be provided to the City of False at a rate at or below the cost of diesel generated electricity and sold to commercial customers at rates competitive with current market rates, providing a stable, flat priced, environmentally sound alternative to the diesel generation currently utilized for energy in the community. The Project Team concluded that with additional grants and private investment a tidal energy project at False Pass is well-positioned to be the first tidal energy project to be developed in Alaska, and the first tidal energy project to be interconnected to an isolated micro grid in the world. A viable project will be a model for similar projects in coastal Alaska.

16 TIDAL AND WAVE POWER↗

Life Cycle Assessment of Methanol from Fossil, Biomass, and Waste Sources, and Its Use as a Marine Fuel in Dual-Fuel Engines

Methanol is gaining interest in the marine sector from energy security and reducing emissions perspective. This study provides a comparative life cycle assessment of methanol as a marine fuel, across GHG and criteria air pollutant emission metrics, when it is used in a dual-fuel engine. Twelve methanol pathways from four different feedstock categories were considered, including (1) cellulosic biomass forest residues and clean pine mix, corn stover, switchgrass, and miscanthus; (2) organic wastes renewable natural gas from wastewater sludge, swine manure, food waste, and landfill gas; (3) fossil resources coal and natural gas (NG); and (4) e-methanol using captured carbon dioxide. When used in a dual-fuel engine with pilot fuel, life cycle GHG emissions for woody biomass-based methanol were approximately 19 gCO 2 e MJ −1 , while emissions from waste-based sources ranged between −154 and 31 gCO 2 e MJ −1 . Methanol from renewable sources showed a GHG reduction potential between 58 and 226% compared to conventional NG-based methanol (122 gCO 2 e MJ −1 ), primarily due to the avoided emissions from conventional waste management. When carbon from process emissions were captured, the reduction could be up to 327%. All pathways exhibited lower NO X , and particulate matter emissions compared to the baseline marine fuel (MGO 0.1% sulfur), while woody biomass and coal pathways had higher SO X emissions.

09 BIOMASS FUELS↗

End-to-end gene fusions and their impact on the production of multifunctional biomass degrading enzymes

Highlights: Black-Right-Pointing-Pointer Multifunctional enzymes offer an interesting approach for biomass degradation. Black-Right-Pointing-Pointer Size and conformation of separate constructs play a role in the effectiveness of chimeras. Black-Right-Pointing-Pointer A connecting linker allows for maximal flexibility and increased thermostability. Black-Right-Pointing-Pointer Genes with functional similarities are the best choice for fusion candidates. -- Abstract: The reduction of fossil fuels, coupled with its increase in price, has made the search for alternative energy resources more plausible. One of the topics gaining fast interest is the utilization of lignocellulose, the main component of plants. Its primary constituents, cellulose and hemicellulose, can be degraded by a series of enzymes present in microorganisms, into simple sugars, later used for bioethanol production. Thermophilic bacteria have proven to be an interesting source of enzymes required for hydrolysis since they can withstand high and denaturing temperatures, which are usually required for processes involving biomass degradation. However, the cost associated with the whole enzymatic process is staggering. A solution for cost effective and highly active production is through the construction of multifunctional enzyme complexes harboring the function of more than one enzyme needed for the hydrolysis process. There are various strategies for the degradation of complex biomass ranging from the regulation of the enzymes involved, to cellulosomes, and proteins harboring more than one enzymatic activity. In this review, the construction of multifunctional biomass degrading enzymes through end-to-end gene fusions, and its impact on production and activity by choosing the enzymes and linkers is assessed.

60 APPLIED LIFE SCIENCES↗

Process intensification of CO 2 capture by low-aqueous solvent

Low-energy solvent-based CO 2 absorption processes have drawn attention as a next-generation post-combustion CO 2 capture technology to reduce CO2 emissions from fossil fuel– or biomass-fired power generation and industrial flue gas streams. A low-aqueous (or water-lean) solvent process may substantially reduce the thermal energy consumption for solvent regeneration. Low-aqueous solvent–based processes are thermally sensitive, requiring a delicate temperature control within the absorber because of the fast exothermic amine-CO 2 reaction and low heat capacity organic diluent. This reaction may result in heat accumulation in a packed absorption column and undesirable CO 2 desorption occurring as the solvent moves through the column, reducing the solvent’s CO 2 capture efficiency if its temperature is not controlled. Using a 3D printed intensified packing device, enhanced heat and mass transfer were demonstrated in an amine-CO 2 scrubbing process using low-aqueous solvent. The multifunctional intensified device facilitates contact of the reactive solvent and gas phases in a single stage and heat removal by a cooling fluid flowing through channels in the interior of the corrugated plates of the device. These functionalities led to effective thermal management along the column via intrastage cooling and significant improvement in CO 2 uptake under a wide range of operating conditions. Intrastage cooling effectively reduced the solvent average temperature along the column by ~10 °C and, as a result, the solvent’s capture efficiency improved by up to 25%.

42 ENGINEERING↗

The Role of Interface Band Alignment in Epitaxial SrTiO 3 /GaAs Heterojunctions

Recent concerns surrounding climate change and the contribution of fossil fuels to greenhouse gas (GHG) emissions have sparked interest and advancements in renewable energy sources including wind, solar, and hydroelectricity. These energy sources, often referred to as “clean energy”, generate no operational onsite GHG emissions. They also offer the potential for clean hydrogen production through water electrolysis, presenting a viable solution to create an environmentally friendly alternative energy carrier with the potential to decarbonize industrial processes reliant on hydrogen. To conduct a full life cycle analysis, it is crucial to account for the embodied emissions associated with renewable and nuclear power generation plants as they can significantly impact the GHG emissions linked to hydrogen production and its derived products. In this work, we conducted a comprehensive analysis of the embodied emissions associated with solar photovoltaic (PV), wind, hydro, and nuclear electricity. We investigated the implications of including plant-embodied emissions in the overall emission estimates of electrolysis hydrogen production and subsequently on the production of synthetic ammonia, methanol, and Fischer– Tropsch (FT) fuels. Results show that average embodied GHG emissions of solar PV, wind, hydro, and nuclear electricity generation in the United States (U.S.) were estimated to be 37, 9.8, 7.2, and 0.3 g CO 2 e/kWh, respectively. Life cycle GHG emissions of electrolytic hydrogen produced from solar PV, wind, and hydroelectricity were estimated as 2.1, 0.6, and 0.4 kg of CO 2 e/kg of H 2 , respectively, in contrast to the zero-emissions often used when the embodied emissions in their construction were excluded. Average life cycle emission estimates (CO 2 e/kg) of synthetic ammonia, methanol, and FT-fuel from solar PV electricity are increased by 5.5, 16, and 49 times, respectively, compared to the case when embodied emissions are excluded. This change also depends on the local irradiance for solar power, which can result in a further increase of GHG emissions by 35–41% in areas of low irradiance or reduce GHG emissions by 21–25% in areas with higher irradiance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technoeconomic Model and Pathway to <$2/kg Green Hydrogen Using Integrated Halide Perovskite Photoelectrochemical Cells

The cost of gray hydrogen produced via fossil fuel-based steam-methane reforming has led the U.S. Department of Energy to specify <$\$$2/kg H 2 as a target for commercially competitive green hydrogen generation methods. Integrated photoelectrochemical cells have been proposed as a solar-to-hydrogen conversion technology. In this paper we describe a technoeconomically feasible pathway to reaching <$\$$2/kg green H 2 using integrated photoelectrochemical cells with halide perovskite photoabsorbers, low-cost conductive barriers, and low precious metal-content catalysts in an aqueous, membrane-separated cell. A base-case solar-to-hydrogen conversion efficiency of 20%, stable lifetime of 10 years, and a combined electrocatalyst-plus-panel cost of $\$$50/m 2 enabled a levelized cost of hydrogen of $\$$2.43/kg, which dropped below $\$$2/kg with improved performance metrics including material cost, improvements in process design, or subsidies. We relate these metrics to lab-scale reports to recommend best research practices for scientists and funding agencies working at this intersection of photovoltaics, electrocatalysis, and surface science.

$1/kg↗

Mechanism of Methane Chemical Looping Combustion with Hematite Promoted with CeO 2

Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion that produces sequestration-ready CO{sub 2} stream, reducing the energy penalty of CO{sub 2} separation from flue gases. An effective oxygen carrier for CLC will readily react with the fuel gas and will be reoxidized upon contact with oxygen. This study investigated the development of a CeO{sub 2}-promoted Fe{sub 2}O{sub 3}-hematite oxygen carrier suitable for the methane CLC process. Composition of CeO{sub 2} is between 5 and 25 wt % and is lower than what is generally used for supports in Fe{sub 2}O{sub 3} carrier preparations. The incorporation of CeO{sub 2} to the natural ore hematite strongly modifies the reduction behavior in comparison to that of CeO{sub 2} and hematite alone. Temperature-programmed reaction studies revealed that the addition of even 5 wt % CeO{sub 2} enhances the reaction capacity of the Fe{sub 2}O{sub 3} oxygen carrier by promoting the decomposition and partial oxidation of methane. Fixed-bed reactor data showed that the 5 wt % cerium oxides with 95 wt % iron oxide produce 2 times as much carbon dioxide in comparison to the sum of carbon dioxide produced when the oxides were tested separately. This effect is likely due to the reaction of CeO{sub 2} with methane forming intermediates, which are reactive for extracting oxygen from Fe{sub 2}O{sub 3} at a considerably faster rate than the rate of the direct reaction of Fe{sub 2}O{sub 3} with methane. These studies reveal that 5 wt % CeO{sub 2}/Fe{sub 2}O{sub 3} gives stable conversions over 15 reduction/oxidation cycles. Lab-scale reactor studies (pulsed mode) suggest the methane reacts initially with CeO{sub 2} lattice oxygen to form partial oxidation products (CO + H{sub 2}), which continue to react with oxygen from neighboring Fe{sub 2}O{sub 3}, leading to its complete oxidation to form CO{sub 2}. The reduced cerium oxide promotes the methane decomposition reaction to form C + H{sub 2}, which continue to react with Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} to form CO/CO{sub 2} and H{sub 2}O. This mechanism is supported by the characterization studies, which also suggest that the formation of carbonaceous intermediates may affect the reaction rate and selectivity of the oxygen carrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel

We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylethane or its alcohol congener, 2-phenoxy-1-phenylethanol, the benzylic site is activated via Ni C–H insertion, followed by beta elimination of the phenoxide leaving group. But in the case of the ketone, 2-phenoxyacetophenone, the polarized carbonyl π system apparently binds directly with the electron rich Ni cathode surface without breaking the aromaticity of the neighboring phenyl ring, leading to rapid cleavage. Substituent steric and electronic perturbations across a broad range of β-O-4 type ethers create a hierarchy of cleavage rates that supports these mechanistic ideas while offering guidance to allow rational design of the catalytic method. Furthermore, on the basis of the new insights, the usage of cosolvent acetone is shown to enable control of product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗