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Catalytic Conditioning and Conversion of Bio-Syngas: Cooperative Research and Development Final Report, CRADA Number CRD-10-418

There is a critical need to increase the carbon yield of the gasification process. To this end, it has been suggested that tars and chars formed as by-products of gasification be re-injected into the gasifier. In this CRADA work facile and inexpensive methods of modifying chars and tars received from Enerkem are studied with the aim of increasing their gasification rate upon re-injection into the gasifier. Adding iron to the char, both in nitrate form and in clay form, speeds the CO 2 gasification of the char (CO 2 + C --> 2CO). It has been more difficult to speed the gasification of tar mixed with char, likely due to clogging of pores, resulting in a reduced accessible surface area.

09 BIOMASS FUELS↗

Low-Temperature Synthesis, Structural Characterization, and Electrochemistry of Ni-Rich Spinel-like LiNi 2– y Mn y O 4 (0.4 ≤ y ≤ 1)

The thermal conversion of chemically delithiated layered Li 0.5 Ni 1-y Mn y O 2 (0.2 ≤ y ≤ 0.5) into spinel-like LiNi 2-y Mn y O 4 (0.4 ≤ y ≤ 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25–300 °C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.

36 MATERIALS SCIENCE↗

Predicting Device Parameters for Dye-Sensitized Solar Cells from Electronic Structure Calculations to Reproduce Experiment.

Given that improvements to the power-conversion efficiency (PCE) of dye-sensitized solar cells (DSSCs) have slowed in recent years, a means to accurately predict the device parameters yielded by trial dyes in silico, without having to synthesize them, would be extremely valuable to speed up the design process. Currently, the best-performing methods of calculating device parameters rely on a set of experimentally determined kinetic coefficients. In practice, it is very difficult to measure these kinetic parameters accurately, limiting the overall accuracy of such predictive methods. This work proposes a model to obtain key parameters such as J(SC), V-OC, and PCE using only the results from density functional theory (DFT) and time-dependent DFT calculations, noting that rates of electron-transfer steps are ultimately linked to the electronic structure of the dye center dot center dot center dot TiO2 working electrode. Six organic DSSC dyes from dissimilar chemical classes (L0, L1, L2, WS-2, WS-92, and C281) were chosen to demonstrate the power of this approach. Their a priori known experimentally determined device performance metrics served to validate our predictions. The greatest absolute error in our predicted PCE values was 0.36% relative to the experiment, while the greatest fractional error was 0.042. This indicates that the proposed model offers a dramatic improvement on previous predictive methods for DSSC device parameters, both in accuracy and in consistency. Moreover, such a predictive model has great potential to be applied to other photovoltaic applications, further enabling the design of novel, highly efficient photoactive materials.

density functional theory↗

Structural and light up-conversion luminescence properties of Er{sup 3+}-Yb{sup 3+}-W{sup 6+} substituted Bi{sub 4}Ti{sub 3}O{sub 12}

The structural and light up-conversion (UC) luminescence properties of W{sup 6+} substituted Bi{sub 3.79}Er{sub 0.03}Yb{sub 0.18}Ti{sub 3-x}W{sub x}O{sub 12} (0 ≤ x ≤ 0.10) ceramics prepared by solid state reaction method have been investigated. X-ray diffraction (XRD) confirms the formation of single phase material with orthorhombic structure. A decrease in the lattice parameters and unit cell volume is observed with increasing W content. Strong UC luminescence at 527, 548 and 662 nm is seen under an excitation of 980 nm for an optimum W content (x = 0.06) and is attributed to the transitions {sup 2}H{sub 11/2} →{sup 4}I{sub 15/2}, {sup 4}S{sub 3/2} →{sup 4}I{sub 15/2} and {sup 4}F{sub 9/2} →{sup 4}I{sub 15/2} respectively. The improved UC luminescence is ascribed to the reduced defects such as oxygen vacancies and change in the crystal field around Er{sup 3+} ions due to B-site (Ti{sup 4+}) substitution with W{sup 6+} ions. Enhanced UC emission is observed for an optimum content of w{sup 6+} in the prepared composition Bi{sub 3.79}Er{sub 0.03}Yb{sub 0.18}Ti{sub 3-x}W{sub x}O{sub 12} for x = 0.06.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Up-conversion luminescent properties of La{sub (0.80−x)}VO{sub 4}:Yb{sub x}, Er{sub 0.20} phosphors

Highlights: • A novel green and red emitting LaVO{sub 4}:Yb{sub x}{sup 3+}, Er{sub 0.20}{sup 3+} phosphors were synthesized. • Their structures, luminescent properties have also been investigated. • Major laser transition for Er{sup 3+} ion is {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2} (525 nm). • These results suggest the possibility as photonic devices. - Abstract: Yb{sup 3+}, Er{sup 3+} co-doped LaVO{sub 4} phosphors were synthesized by solid state reaction method. Yb{sup 3+} concentrations were changed from 0.01 to 0.20 mol for the fixed Er{sup 3+} concentration at 0.2 mol. The crystalline structure of samples was investigated by X-ray diffraction (XRD). The composition was investigated by X-ray photoelectron spectroscopy (XPS) analysis. The surface morphology was observed by scanning electron microscope (SEM). The red and green up-conversion emissions were observed in Yb{sup 3+}, Er{sup 3+} co-doped LaVO{sub 4} phosphors under the excitation of 980 nm laser diode. Several emissions in green and red regions of the spectrum were observed near 525 nm, 553 nm and 659 nm radiated by {sup 2}H{sub 11/2} → {sup 4}I{sub 15/2}, {sup 4}S{sub 3/2} → {sup 4}I{sub 15/2}, and {sup 4}F{sub 3/2} → {sup 4}I{sub 15/2} transitions, respectively.

36 MATERIALS SCIENCE↗

A Low-Temperature, Solution-Processable, Cu-Doped Nickel Oxide Hole-Transporting Layer via the Combustion Method for High-Performance Thin-Film Perovskite Solar Cells

The promising photophysical properties of the emerging organometallic halide perovskites, such as intense broadband absorption, high charge carrier mobility, and long charge diffusion length, have enabled the rapid development in solar cells reaching over 20% power conversion effi ciency (PCE) recently. Especially, the low material cost and facile solution processability of perovskites are very attractive as next-generation photovoltaic materials for sustainable energy.

14 SOLAR ENERGY↗

Accelerated Synthesis of Ordered Mesoporous Carbons Using Plasma

Conventional ordered mesoporous carbon (OMC) production usually requires long processing times in the carbonization step to achieve desired temperatures through controlled ramps. To enable expedited materials discovery, developing advanced manufacturing capability with significantly improved throughput is highly desired. Current approaches for accelerating the synthesis of OMCs include using microwave and Joule heating. However, both methods rely on the introduction of additional components, such as microwave absorbers and electrically conductive agents, within the bulk materials to impart the ability to reach high carbonization temperatures. This work demonstrates accelerated synthesis and functionalization of OMCs through the use of a dielectric barrier discharge plasma, where carbonization can be accomplished within 15 min using 30 W plasma sources, representing more than an order of magnitude increase in polymer-to-carbon conversion kinetics compared to that of a traditionally pyrolyzed analogue. Particularly, the ability of performing rapid carbonization without the use of additional substrates within the OMC precursor systems is advantageous. A systematic investigation of how plasma power, time, and gas atmosphere impact the resulting OMC pore textures and properties is performed, demonstrating the broad applicability of plasma-enabled carbonization methods. Furthermore, we demonstrate that the plasma treatment strategy can be extended to incorporate heteroatoms into the carbon framework by introducing ammonia gas, resulting in OMCs with a nitrogen content up to 4.7 at %, as well as non-Pluronic templating systems for synthesizing OMC with pore sizes larger than 10 nm. As employing a plasma source for materials pyrolysis is an industrially relevant approach, our system can be extended toward scaled synthesis of OMCs with much faster production rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sn doping on partially dealuminated Beta zeolite by solid state ion exchange for 5‐hydroxymethylfurfural ( 5‐HMF ) production from glucose

Abstract BACKGROUND The conversion of glucose into 5‐hydroxymethylfurfural (5‐HMF) involves the isomerization of glucose to fructose catalyzed by Lewis acid and subsequent dehydration of fructose catalyzed by Brönsted acid. In this work, in order to obtain a high yield of 5‐HMF, a series of Sn‐Al‐Beta catalysts containing both Lewis and Brönsted acid sites were prepared by a convenient solid state ion exchange (SSIE) method using partially dealuminated Beta zeolite and tin(II) acetate. RESULTS The obtained bifunctional catalysts were investigated for one‐pot production of 5‐HMF from glucose in the ionic liquid (IL) [C 4 mim]Cl. Among various catalysts, Sn‐Al‐Beta‐ 4 ‐ 8 exhibited the best catalytic performance, giving a 5‐HMF yield of 54% under optimal reaction conditions (393 K, 2 h), along with a glucose conversion of 81%. The Sn‐Al‐Beta‐ 4‐8 catalyst and IL were regenerated by the extraction of 5‐HMF, and the reactivity was reserved after five runs of recycling. In addition to glucose, the Sn‐Al‐Beta‐ 4‐8 /[C 4 mim]Cl system was also proven to have the potential to effectively convert other carbohydrates into 5‐HMF. CONCLUSION The results suggested that the catalyst is convenient to prepare and has preferable efficiency and stability in the conversion of carbohydrates into 5‐HMF. © 2022 Society of Chemical Industry (SCI).

Zhang, Wei↗

Multifunctional Conjugated Ligand Engineering for Stable and Efficient Perovskite Solar Cells

Surface passivation is an effective way to boost the efficiency and stability of perovskite solar cells (PSCs). However, a key challenge faced by most of the passivation strategies is reducing the interface charge recombination without imposing energy barriers to charge extraction. Here, a novel multifunctional semiconducting organic ammonium cationic interface modifier inserted between the light-harvesting perovskite film and the hole-transporting layer is reported. It is shown that the conjugated cations can directly extract holes from perovskite efficiently, and simultaneously reduce interface non-radiative recombination. Together with improved energy level alignment and the stabilized interface in the device, a triple-cation mixed-halide medium-bandgap PSC with an excellent power conversion efficiency of 22.06% (improved from 19.94%) and suppressed ion migration and halide phase segregation, which lead to a long-term operational stability, is demonstrated. Finally, this strategy provides a new practical method of interface engineering in PSCs toward improved efficiency and stability.

36 MATERIALS SCIENCE↗

Monolithic Photoelectrochemical CO 2 Reduction Producing Syngas at 10% Efficiency

We report increasing anthropogenic carbon dioxide emissions have prompted the search for photoelectrochemical (PEC) methods of converting CO 2 to useful commodity products, including fuels. Ideally, such PEC approaches will be sustained using only sunlight, water, and CO 2 as energetic and reactant inputs. However, low peak conversion efficiencies (< 5%) have made commercialization of fully-integrated PEC devices prohibitive. Here, a 4 cm 2 monolithic PEC device exceeding 10% solar-to-fuel efficiency with principal fuel products of carbon monoxide and hydrogen is reported. The corresponding solar-to-CO and solar-to-H 2 efficiencies are 7% and 3.5%, respectively. Screening of a range of operating conditions reveals a tunable product mixture of H 2 and CO using a gold electrocatalyst. Accordingly, it is shown that device optimization yields a H 2 -to-CO ratio of 1:2 commonly present in synthesis gas (syngas). Notably, the modularity and facile fabrication of this device permit the incorporation of a broad array of materials for various applications. For example, the electrocatalyst may easily be swapped to target a different set of products.

36 MATERIALS SCIENCE↗

The method of imbedded Lagrangian element to estimate wave power absorption by some submerged devices

A simple approach is described to estimate the wave power absorption potential of submerged devices known to cause wave focusing and flow enhancement. In particular, the presence of a flow-through power take-off (PTO) system, such as low-head turbines, can be accounted for. The wave radiation characteristics of an appropriately selected Lagrangian element (LE) in the fluid domain are first determined. In the limit of a vanishing mass, the LE reduces to a patch of distributed normal dipoles. Here, the hydrodynamic coefficients of this virtual object are then input in a standard equation of motion where the effect of the PTO can be represented, for example, as a dashpot damping term. The process is illustrated for a class of devices recently proposed by Carter and Ertekin (2011), although in a simplified form. Favorable wave power absorption is shown for large ratios of the LE wave radiation coefficient over the LE added mass coefficient. Under optimal conditions, the relative flow reduction from the PTO theoretically lies between 0.50 and 1/√2≈ 0.71, with lower values corresponding to better configurations. Wave power capture widths, the sensitivity of results to PTO damping and sample spectral calculations at a typical site in Hawaiian waters are proposed to further illustrate the versatility of the method.

16 TIDAL AND WAVE POWER↗

Pyrolysis of high-density polyethylene: Degradation behaviors, kinetics, and product characteristics

Pyrolysis is a promising technology for converting plastic waste into valuable raw materials while offering a potential solution to the global plastic pollution crisis. In this study, the thermal pyrolysis of high-density polyethylene (HDPE) is investigated in a drop tube reactor under nearly isothermal conditions. The impact of reaction temperature and gas/volatile residence time on carbon conversion and product distribution is examined across a range of 500–900°C and 3.6–32.2s, respectively. Non-condensable gas products detected by online mass spectrometry are H 2 , CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , and C 3 H 8 . At elevated temperatures and prolonged residence time, H 2 yield reaches as high as 8.6 wt% of the initial HDPE mass due to intensified cracking reactions of C 2 –C 3 hydrocarbons and long-chain aliphatic compounds. Consequently, pyrolysis tars consist mainly of polycyclic aromatic hydrocarbons (PAHs) with 5–7 rings, accompanied by visible coke deposition within the reactor. HDPE decomposition to volatiles is an endothermic process and it is complete at a temperature between 492°C and 525°C, depending on the heating rate employed, from non-isothermal thermogravimetric analysis and differential scanning calorimetry (TGA-DSC) measurements. The thermal degradation of HDPE pellets follows the two-dimensional nucleation growth model for conversion levels up to 0.8 with an apparent activation energy of 259–270 kJ/mol and a pre-exponential factor of 4.83 × 10 17 –1.37 × 10 19 min -1 , determined from various isoconversional methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, along with Criado's master plots. Further, these findings provide valuable insights into optimizing process parameters and refining reactor design for pyrolysis, which can be integrated with gasification and reforming processes to enhance hydrogen production on a larger scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning domain size and crystallinity in isoindigo/PCBM organic solar cells via solution shearing

Despite having achieved the long sought-after performance of 10% power conversion efficiency, high performance organic photovoltaics (OPVs) are still mostly constrained to lab scale devices fabricated by spin coating. Efforts to produce printed OPVs lag considerably behind, and the sensitivity to different fabrication methods highlights the need to develop a comprehensive understanding of the processing-morphology relationship in printing methods. Here we present a systematic experimental investigation of a model low bandgap polymer/fullerene system, poly-isoindigo thienothiophene/PC 61 BM, using a lab-scale analogue to roll-to-roll coating as the fabrication tool in order to understand the impact of processing parameters on morphological evolution. We report that domain size and polymer crystallinity can be tuned by a factor of two by controlling the temperature and coating speed. Lower fabrication temperature simultaneously decreased the phase separation domain size and increased the relative degree of crystallinity in those domains, leading to improved photocurrent. We conclude that domain size in isoindigo/PCBM is dictated by spontaneous phase separation rather than crystal nucleation and growth. Moreover we present a model to describe the temperature dependence of domain size formation in our system, which demonstrates that morphology is not necessarily strictly dependent on the evaporation rate, but rather on the interplay between evaporation and diffusion during the printing process.

14 SOLAR ENERGY↗

Thermal engineering of FAPbI 3 perovskite material via radiative thermal annealing and in situ XRD

Lead halide perovskites have emerged as successful optoelectronic materials with high photovoltaic power conversion efficiencies and low material cost. However, substantial challenges remain in the scalability, stability and fundamental understanding of the materials. Here we present the application of radiative thermal annealing, an easily scalable processing method for synthesizing formamidinium lead iodide (FAPbI 3 ) perovskite solar absorbers. Devices fabricated from films formed via radiative thermal annealing have equivalent efficiencies to those annealed using a conventional hotplate. By coupling results from in situ X-ray diffraction using a radiative thermal annealing system with device performances, we mapped the processing phase space of FAPbI 3 and corresponding device efficiencies. Our map of processing-structure-performance space suggests the commonly used FAPbI 3 annealing time, 10 min at 170 degrees C, can be significantly reduced to 40 s at 170 degrees C without affecting the photovoltaic performance. Lastly, the Johnson-Mehl-Avrami model was used to determine the activation energy for decomposition of FAPbI 3 into PbI 2 .

14 SOLAR ENERGY↗

Substituent effects in a series of 1,7-C[subscript 60](R[subscript F])[subscript 2] compounds (R[subscript F] = CF[subscript 3], C[subscript 2]F[subscript 5], n-C[subscrip 3]F[subscript 7], i-C[subscript 3]F[subscript 7], n-C[subscript 4]F[subscript 9], s-C[subscript 4]F[subscript 9], n-C[subscript 8]F[subscript 17]): electron affinities, reduction potentials and E(LUMO) values are not always correlated

A series of seven structurally-similar compounds with different pairs of R{sub F} groups were prepared, characterized spectroscopically, and studied by electrochemical methods (cyclic and square-wave voltammetry), low-temperature anion photoelectron spectroscopy, and DFT calculations (five of the compounds are reported here for the first time). This is the first time that a set of seven R{sub F} groups have been compared with respect to their relative effects on E{sub 1/2}(0/-), electron affinity (EA), and the DFT-calculated LUMO energy. The compounds, 1,7-C{sub 60}(R{sub F}){sub 2} (R{sub F} = CF{sub 3}, C{sub 2}F{sub 5}, i-C{sub 3}F{sub 7}, n-C{sub 3}F{sub 7}, s-C{sub 4}F{sub 9}, n-C{sub 4}F{sub 9} and n-C{sub 8}F{sub 21}), were found to have statistically different electron affinities (EA), at the {+-}10 meV level of uncertainty, but virtually identical first reduction potentials, at the {+-}10 mV level of uncertainty. The lack of a correlation between EA and E{sub 1/2}(0/-), and between E(LUMO) and E{sub 1/2}(0/-), for such similar compounds is unprecedented and suggests that explanations for differences in figures of merit for materials and/or devices that are based on equating easily measurable E{sub 1/2}(0/-) values with EAs or E(LUMO) values should be viewed with caution. The solubilities of the seven compounds in toluene varied by nearly a factor of six, but in an unpredictable way, with the C{sub 2}F{sub 5} and s-C{sub 4}F{sub 9} compounds being the most soluble and the i-C{sub 3}F{sub 7} compound being the least soluble. The effects of the different R{sub F} groups on EAs, E(LUMO) values, and solubilities should help fluorine chemists choose the right R{sub F} group to design new materials with improved morphological, electronic, optical, and/or magnetic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and characterization of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with a wide range of compositions

We describe the synthesis and characterization of wurtzite (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with a wide range of compositions and a focus on properties relevant for solar fuel generation. (Ga 1-x Zn x )(N 1-x O x ), a solid solution of GaN and ZnO, is an intriguing material because it exhibits composition-dependent visible absorption even though the parent semiconductors absorb in the UV. When functionalized with co-catalysts, (Ga 1-x Zn x )(N 1-x O x ) is also capable of water splitting under visible irradiation. Here, we examine the synthesis of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals to understand how they form by nitridation of ZnO and ZnGa 2 O 4 nanocrystalline precursors. We find that the ZnO precursor is critical for the formation of crystalline (Ga 1-x Zn x )(N 1-x O x ) at 650 °C, consistent with a mechanism in which wurtzite (Ga 1-x Zn x )(N 1-x O x ) nucleates topotactically on wurtzite ZnO at an interface with ZnGa 2 O 4 . Using this information, we expand the range of compositions from previously reported 0.30 ≤ x ≤ 0.87 to include the low-x and high-x ends of the range. The resulting compositions, 0.06 ≤ x ≤ 0.98, constitute the widest range of (Ga 1-x Zn x )(N 1-x O x ) compositions obtained by one synthetic method. We then examine how the band gap depends on sample composition and find a minimum of 2.25 eV at x = 0.87, corresponding to a maximum possible solar-to-H 2 power conversion efficiency of 12%. Finally, we examine the photoelectrochemical (PEC) oxidation behavior of thick films of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with x = 0.40, 0.52, and 0.87 under visible illumination. (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with x = 0.40 exhibit solar PEC oxidation activity that, while too low for practical applications, is higher than that of bulk (Ga 1-x Zn x )(N 1-x O x ) of the same composition. The highest photocurrents are observed at x = 0.52, even though x = 0.87 absorbs more visible light, illustrating that the observed photocurrents are a result of an interplay of multiple parameters which remain to be elucidated. This set of characterizations provides information useful for future studies of composition-dependent PEC properties of nanoscale (Ga 1-x Zn x )(N 1-x O x ).

36 MATERIALS SCIENCE↗

Tunnel Junction Development Using Hydride Vapor Phase Epitaxy

We demonstrate for the first time III-V tunnel junctions grown using hydride vapor phase epitaxy (HVPE) with peak tunneling currents >8 A/cm 2 , sufficient for operation of a multijunction device to several hundred suns of concentration. Multijunction solar cells rely on tunneling interconnects between subcells to enable series connection with minimal voltage loss, but tunnel junctions have never been shown using the HVPE growth method. HVPE has recently reemerged as a low-cost growth method for high-quality III-V materials and devices, including the growth of high-efficiency III-V solar cells. We previously showed single-junction GaAs solar cells with conversion efficiencies of ~24% with a path forward to equal or exceed the practical efficiency limits of crystalline Si. Moving to a multijunction device structure will allow for even higher efficiencies with minimal impact on cost, necessitating the development of tunnel interconnects. Here in this paper, we demonstrate the performance of both isolated HVPE-grown tunnel junctions, as well as single-junction GaAs solar cell structures with a tunnel junction incorporated into the contact region. We observe no degradation in device performance compared to a structure without the added junction.

14 SOLAR ENERGY↗

Inorganic Materials and Assembly Techniques for Flexible and Stretchable Electronics

In recent years, important progress has been made in developing design strategies, materials, and associated assembly techniques that provide empowering approaches to electronics with unconventional formats, ones that allow useful but previously hard to realize attributes of function. Notable examples of the progress made include: light weight, large area, high performance electronics, optics, and photonics; electronic and optical systems with curvilinear shapes and capacities for accommodating demanding forms of mechanical flexure; new device form factors for use in sensing and imaging; the integration of high performance electronics in 3-D with demanding nanometer design rules; functional bioresponsive electronics; and advanced hybrid materials systems for lighting, energy storage, and photovoltaic energy conversion. In this report we highlight advances that are enabling such promising capabilities in technology-specifically, the fabrication of device elements using high performance inorganic electronic materials joined with printing and transfer methods to effect their integration within functional modules. Here, we emphasize in this review considerations of the design strategies and assembly techniques that, when taken together, circumvent limitations imposed by approaches that integrate circuit elements within compact, rigid, and essentially planar form factor devices, and provide a transformational set of capabilities for high performance flexible/stretchable electronics.

36 MATERIALS SCIENCE↗