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At least 19 records

Design and Analysis of Short Period 2G-HTS Undulators

Recent advancements in second-generation high-temperature superconducting (2G-HTS) materials have opened new possibilities for superconducting undulator (SCU) technology, particularly in achieving shorter periods and higher magnetic fields. Here, this paper presents the design and analysis of a short-period, as small as 10 mm, 2G-HTS undulator, focusing on magnetic performance, mechanical force minimization, and quench protection. A force-balanced coil pack design is introduced to significantly reduce mechanical stresses on the conductors, eliminating the need for heavy support structures. Rapid prototyping techniques such as3D printing is employed to refine the design for scalability and manufacturability. Correction schemes for end-field effects are developed using a combination of 2G-HTS tapes and NbTi conductors to optimize field integrals. Simulation results demonstrated that optimized magnetic performance and enhanced mechanical stability, positioning 2G-HTS undulators as promising candidates for storage ring and free-electron based light sources.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced Second Generation (2G) High Temperature Superconducting (HTS) wire for Electric Motor Applications

This project focused on the development of a revolutionary Second Generation (2G) high temperature superconducting (HTS) wire engineered specifically to meet the requirements for a new generation of high temperature superconducting electric machines. This novel design combined a roll-to-roll irradiation process to enhance the performance of the HTS wire in the presence of strong magnetic fields (improved flux pinning) with an innovative process to incorporate multiple HTS layers within a single 2G wire.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Impact of non-irrigation on 1G and 2G bioethanol potential of oilcane feedstock: A field to fuel pipeline study

This study evaluates the bioethanol potential in response to irrigation (IR) and non-irrigation (NIR) of oilcane (OC) during a seasonal drought prior harvest. The juice was extracted through mechanical pressing of stems and fermented by Ethanol Red® yeast to produce first-generation bioethanol. Hydrothermal pretreatment followed by enzymatic hydrolysis of bagasse was performed to produce monomeric sugars from structural carbohydrates. The hydrolysates were fermented with engineered yeast for second-generation bioethanol production. The irrigated oilcane juice (276.3 ± 8.9 g/L) constitutes higher sugar concentrations than non-irrigated oilcane juice (236.5 ± 2.2 g/L). The enzymatic hydrolysis of IR-OC and NIR-OC pretreated bagasse yielded similar concentrations of 247.5 ± 2.22 and 249.7 ± 4.98 g/L fermentable sugars. Industry-relevant bioethanol titers of ≥99 g/L and ≥75 g/L were achieved from juice and hydrolysates, respectively. Therefore, the non-irrigation regime did not impact the 1G and 2G bioethanol titers. However, the overall bioethanol yield can be lower due to the reduction of stem yield (8 %) per hectare.

09 BIOMASS FUELS↗

Probing the Irradiation Defects in Enhanced 2G High Temperature Superconducting Wire

In this paper, we present a detailed investigation of the atomic and chemistry structures of irradiation defects in AMSC’s second generation (2G) HTS coil wire by using aberration-corrected scanning transmission electron microscopy (AC-STEM) coupled with atomic resolution electron energy loss spectroscopy (EELS). A 1.2μm thick Dy-doped YBCO films was deposited onto Ni(5at%)W RABiTS substrate by metal organic deposition (MOD) process [6]. The ion irradiation was carried out at Brookhaven National Laboratory using the tandem Van de Graaff accelerators with 18-MeV Au 5+ ions to a dose of 2×10 11 Au/cm 2 along the c-axis of YBCO film. Prior to the irradiation, the coil wire sample has a 77 K, self-field Ic of around 385 A/cm-w. In comparison, the value decreased to 320 A/cm-w after irradiation.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Data for A Chemical-Free Pretreatment for Biosynthesis of Bioethanol and Lipids from Lignocellulosic Biomass: An Industrially Relevant 2G Biorefinery Approach

A wide range of inorganic and organic chemicals are used during the pretreatment and enzymatic hydrolysis of lignocellulosic biomass to produce biofuels. Developing an industrially relevant 2G biorefinery process using such chemicals is challenging and requires more unit operations for downstream processing. A sustainable process has been developed to achieve industrially relevant titers of bioethanol with significant ethanol yield. The pretreatment of sorghum biomass was performed by a continuous pilot-scale hydrothermal reactor followed by disk milling. Enzymatic hydrolysis was performed without washing the pretreated biomass. Moreover, citrate buffer strength was reduced to 100-fold (50 mM to 0.5 mM) during the enzymatic hydrolysis. Enzymatic hydrolysis at 0.5 mM citrate buffer strength showed that significant sugar concentrations of 222 ± 2.3 to 241 ± 2.3 g/L (glucose + xylose) were attained at higher solids loadings of 50 to 60% (w/v). Furthermore, hydrolysates were fermented to produce bioethanol using two different xylose-fermenting Saccharomyces cerevisiae strains and a co-culture of xylose-fermenting and non-GMO yeast cultures. Bioethanol titer of 81.7 g/L was achieved with an ethanol yield of 0.48 gp/gs. Additionally, lipids were produced using the oleaginous yeast Rhodosporidium toruloides , yielding 13.2 g/L lipids with cellular lipid accumulation of 38.5% w/w from 100 g/L of sugar concentration. In summary, reducing the strength of the citrate buffer during enzymatic hydrolysis and omitting inorganic chemicals from the pretreatment process enhances the fermentability of hydrolysates and can also reduce operating costs.

Conversion↗

Data for Impact of Non-Irrigation on 1G and 2G Bioethanol Potential of Oilcane Feedstock: A Field to Fuel Pipeline Study

This study evaluates the bioethanol potential in response to irrigation (IR) and non-irrigation (NIR) of oilcane (OC) during a seasonal drought prior harvest. The juice was extracted through mechanical pressing of stems and fermented by Ethanol Red® yeast to produce first-generation bioethanol. Hydrothermal pretreatment followed by enzymatic hydrolysis of bagasse was performed to produce monomeric sugars from structural carbohydrates. The hydrolysates were fermented with engineered yeast for second-generation bioethanol production. The irrigated oilcane juice (276.3 ± 8.9 g/L) constitutes higher sugar concentrations than non-irrigated oilcane juice (236.5 ± 2.2 g/L). The enzymatic hydrolysis of IR-OC and NIR-OC pretreated bagasse yielded similar concentrations of 247.5 ± 2.22 and 249.7 ± 4.98 g/L fermentable sugars. Industry-relevant bioethanol titers of ≥99 g/L and ≥75 g/L were achieved from juice and hydrolysates, respectively. Therefore, the non-irrigation regime did not impact the 1G and 2G bioethanol titers. However, the overall bioethanol yield can be lower due to the reduction of stem yield (8 %) per hectare.

Biomass Analytics↗

Integration of Superconducting Magnetic Energy Storage (SMES) Systems Optimized with Second-Generation, High-Temperature Superconducting (2G-HTS) Technology with a Major Fossil-Fueled Asset

Utility companies and fossil fueled generation assets are seeking combinations of “hybrid energy storage” to allow power to be provided in advance of, and to otherwise complement, peaking natural gas-fired generation. American Maglev Technology of Florida Inc. (AMT) learned during the Phase I program based on interactions with NRG Energy (NRG) that energy storage such as superconducting magnetic energy storage (SMES) can qualify as a Black Start unit in most markets, ensuring orderly re-start of grid operations and fossil fueled power plants and serving as an important asset of hybrid energy storage technology. In conjunction with the University of Houston (UH), AMT and NRG are working together to scale up low-cost, high- efficiency, second-generation high-temperature superconducting (2G-HTS) technology for deployment across several markets, with a primary focus on the commercial development of utility grid-scale SMES (g-SMES) systems. Ultimately the program confirmed that the novel g-SMES design can meet the performance and financial requirements of the fossil power plant industry, while exhibiting continuous grid-voltage regulation; cost-effective, peak-hour energy storage with almost infinite life; increased input/output efficiency; and the capability to undergo millions of charging cycles, without degradation, representing a significant improvement over lithium ion and other conventional storage technologies. We believe wide scale deployment of this technology is feasible and practical when compared to the higher life cycle cost and relatively short lifespan of chemical batteries. Based on these findings, the future for deployment of SMES at many fossil-fueled power plants exceeding 100MW capability is bright. Further de-risking g-SMES technology would pave the way for the construction of a subscale prototype. Eventually, scaled-down versions of SMES are expected to be competitive with the multi-billion-dollar lithium-ion market for a wide range of commercial, industrial, and transportation uses. There is long-term potential for commercialization and widespread deployment of this disruptive technology, which would spawn a new worldwide supply chain and create domestic, high-tech manufacturing jobs in the green industry.

20 FOSSIL-FUELED POWER PLANTS↗

A Chemical-Free Pretreatment for Biosynthesis of Bioethanol and Lipids from Lignocellulosic Biomass: An Industrially Relevant 2G Biorefinery Approach

A wide range of inorganic and organic chemicals are used during the pretreatment and enzymatic hydrolysis of lignocellulosic biomass to produce biofuels. Developing an industrially relevant 2G biorefinery process using such chemicals is challenging and requires more unit operations for downstream processing. A sustainable process has been developed to achieve industrially relevant titers of bioethanol with significant ethanol yield. The pretreatment of sorghum biomass was performed by a continuous pilot-scale hydrothermal reactor followed by disk milling. Enzymatic hydrolysis was performed without washing the pretreated biomass. Moreover, citrate buffer strength was reduced to 100-fold (50 mM to 0.5 mM) during the enzymatic hydrolysis. Enzymatic hydrolysis at 0.5 mM citrate buffer strength showed that significant sugar concentrations of 222 ± 2.3 to 241 ± 2.3 g/L (glucose + xylose) were attained at higher solids loadings of 50 to 60% (w/v). Furthermore, hydrolysates were fermented to produce bioethanol using two different xylose-fermenting Saccharomyces cerevisiae strains and a co-culture of xylose-fermenting and non-GMO yeast cultures. Bioethanol titer of 81.7 g/L was achieved with an ethanol yield of 0.48 gp/gs. Additionally, lipids were produced using the oleaginous yeast Rhodosporidium toruloides, yielding 13.2 g/L lipids with cellular lipid accumulation of 38.5% w/w from 100 g/L of sugar concentration. In summary, reducing the strength of the citrate buffer during enzymatic hydrolysis and omitting inorganic chemicals from the pretreatment process enhances the fermentability of hydrolysates and can also reduce operating costs.

Deshavath, Narendra Naik↗

BCS-BEC crossover in a (t 2g ) 4 excitonic magnet

The condensation of spin-orbit-induced excitons in t 2 g 4 electronic systems is attracting considerable attention. At large Hubbard U , antiferromagnetism was proposed to emerge from the Bose-Einstein Condensation (BEC) of triplons ( J eff = 1 ). Furthermore, we show that even at intermediate U regimes, the spin-orbit exciton condensation is possible leading also to staggered magnetic order. The canonical electron-hole excitations (excitons) transform into local triplon excitations at large U , and this BEC strong coupling regime is smoothly connected to the intermediate U excitonic insulator region. We solved the degenerate three-orbital Hubbard model with spin-orbit coupling ( λ ) in one dimension using the density matrix renormalization group, while in two dimensions we use the Hartree-Fock approximation (HFA). Employing these techniques, we provide the full λ versus U phase diagrams for both one- and two-dimensional lattices. Our main result is that at intermediate Hubbard U , increasing λ at fixed U the system transitions from an incommensurate spin-density-wave metal to a Bardeen-Cooper-Schrieffer (BCS) excitonic insulator, with coherence length r coh of O ( a ) and O ( 10 a ) in 1 d and 2 d , respectively, with a being the lattice spacing. Further increasing λ , the system eventually crosses over to the BEC limit (with r coh ≪ a ).

1-dimensional systems↗

Raman signatures from age-dating PuO 2 since last calcination

The self-irradiation of PuO 2 has been shown to affect the attributes of fifteen vibrational bands in the Raman spectrum. The vibrational bands correspond to the Raman allowed vibrational mode T 2g , overtones, defects, and bands from electronic origin. Defects in the crystal lattice from low-calcination temperature and alpha decay origins are responsible for the changes in the band attributes (band position, full-width half maximum (FWHM), intensity). Crystal lattice defects are also responsible for the growth of the defect bands. The temporal behavior of the vibrational bands can be used to estimate the age of the material since last calcination. Laser annealing was used to reset the material to full crystallinity prior to the aging study. 240 PuO 2 , with an alpha decay rate of 3.67 greater than the decay rate of 239 PuO 2 , was primarily used to assess the alpha decay-induced damage within 3 years. The aging study focused on the time-dependent properties of the T 2g band and the growth of defect bands. The FWHM of the T 2g band and the ratio of the areas of the defect bands/T 2g band were measured through a time period in excess of 3 years. The data from this study were found very close to the data describing the temporal evolution of the lattice constant measured with the X-ray diffraction (XRD) technique. The local physical properties of the material measured with Raman spectroscopy and the lattice parameter constant measured with XRD indicates a strong correlation between the two techniques. Although both techniques provide similar age-dating information, in contrast to the few milligram quantities required for XRD, Raman spectroscopy requires a 10 µm diameter PuO 2 particle to provide an estimate of the material age since last calcination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The effects of thickness, polarization, and strain on vibrational modes of 2D Fe 3 GeTe 2

In this study, we investigated the effects of thickness, light polarization, and strain on the Raman spectra of two-dimensional (2D) Fe 3 GeTe 2 (FGT) crystals synthesized via chemical vapor transport. The crystals are thoroughly characterized using a combination of microscopic, diffraction, and spectroscopic techniques. Particularly, a systematic angle-resolved polarized Raman spectroscopy study reveals a clear polarization dependence of the Raman intensity in both parallel and crossed polarization directions, with the $A$$^{1}_{g}$ mode completely disappearing in the crossed polarization direction. The angle-dependent intensity of both the $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes in parallel polarization and the intensity of the $E$$^{2}_{2g}$ mode in the crossed polarization remain constant at all angles. These findings align with predictions from Raman tensor analysis, providing compelling evidence for the unambiguous assignment of the $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes to specific peaks observed in the Raman spectrum of FGT, resolving existing confusion in the literature regarding their assignment. Furthermore, we examine the effect of strain on the Raman spectrum of 2D FGT in-situ using a bending device. Our study, conducted on a monolayer to few-layer 2D FGT deposited onto polyethylene terephthalate and subjected to outward (inward), i.e., tensile (compressive) bending, demonstrates appreciable downshifting (upshifting) of the Raman peak position of both $A$$^{1}_{g}$ and $E$$^{2}_{2g}$ modes. Furthermore, these findings are particularly significant given that strain engineering represents an effective approach to modulate the magnetic properties of FGT and other 2D magnetic materials.

2D materials↗

Boron isotopic analysis in bulk silicate materials using the Neoma MS/MS MC-ICP-MS

Boron (B) isotopes are a valuable tracer with applications ranging from geological, environmental, and nuclear studies because B isotopic fractionation is highly sensitive to chemical processes yielding distinct isotopic trends in natural and anthropogenic systems. Despite this wide applicability, there remain relatively few measurements on well-described reference materials and in some cases, poor agreement between various methods. We report a method for boron isotope ratio measurement in solution on the Neoma MS/MS MC-ICP-MS specifically targeting bulk silicates. We evaluate the performance of the method and instrument as it relates to the measurement of the absolute boron isotope ratio ( 10 B/ 11 B). The results indicate that the method produces data in agreement with literature values and that the sample–standard bracketing technique is appropriate for the Neoma MS/MS MC-ICP-MS which has been in use for decades on previous generation instruments. Careful tuning of the MS/MS lenses is required to obtain precision comparable to non MS/MS equipped MC-ICP-MS. With careful tuning, internal and external precisions of ∼0.3‰ were achieved. However, when the MS/MS is not properly tuned external precisions exceed 3‰. Nevertheless, our results for IAEA B-6, BCR-2, BHVO-2 and W-2a reference materials overlap the 1σ range of previously reported 10 B/ 11 B. Data are reported for total boron quantities down to a few tens of nanograms. Our procedure yielded blanks as low as 3 ng but up to 29 ng, making blank corrections important for small samples sizes in the few 10s of nanogram range. We report B isotope ratios for AGV-2G, SL-1G, GSC-2G, GSD-2G, GSE-2G, RLS-132, RLS-140, NKT-1G, and T1-G glass reference materials that have not been previously reported in the literature.

Scott, Sean R. [Pacific Northwest National Laborat↗

Data for Optimization of Pre-Commercial Enzymes Dosage for a Potential Lignocellulosic Biorefinery

Lignocellulolytic enzymes remain one of the primary cost constraints in second-generation (2G) ethanol biorefineries. Achieving efficient hydrolysis of structural carbohydrates with minimal enzyme dosage, maintaining slurry fermentability for industrially relevant ethanol titers, and maximizing ethanol yield per ton of biomass are among the major challenges in 2G processes. In this study, we optimized the dosages of pre-commercial cellulase (NS22257) and hemicellulase (NS22244) on pilot-scale, hydrothermally pretreated lignocellulosic substrates. Enzyme dosages were evaluated at three levels: 20 mg of cellulase with 7.25 mg of hemicellulase (ED-1), 40 mg with 14.5 mg (ED-2), and 60 mg with 21.75 mg (ED-3). As expected, the highest sugar yields were obtained with ED-3; however, for sweet sorghum, oilcane, and miscanthus, sugar yields from ED-2 and ED-3 were not significantly different (p < 0.05). For example, sweet sorghum produced 123.78 ± 1.54 g L−1 and 125.76 ± 0.46 g L−1 of total sugars (glucose and xylose) with ED-2 and ED-3, respectively. Although energycane exhibited a statistically significant difference between ED-2 and ED-3, the incremental gain with ED-3 was modest, increasing sugar release by only 9.02 g L−1 relative to ED-2. Importantly, ED-1 resulted in sugar yields of 88.88 ± 3.64 to 106.86 ± 1.21 g L−1, sufficient to achieve ethanol titers ≥40 g L−1, the threshold required for industrial relevance. A semi-integrated bioprocess validated this outcome, producing 42.09 ± 2.38 g L−1 ethanol and an estimated yield of 213.38 L of ethanol per dry ton of pretreated biomass, requiring only 20.83 L of cellulase and 6.25 L of hemicellulase per ton. Remarkably, these enzyme dosages were approximately tenfold lower than those reported in prior studies.

Energycane↗

Deacetylation and Mechanical Refining Pathway for the Bioconversion of Sugarcane Bagasse

Advancing lignocellulose biorefining is imperative for the deployment of cellulosic (2G) biofuels. This work investigates the tailoring of the alkaline deacetylation and mechanical refining (DMR) pathway for the bioconversion of sugarcane bagasse. Experiments are conducted at laboratory and pilot scales, varying the pretreatment conditions (70–92 °C; 48–100 g NaOH /kg) and the mechanical refining technologies (PFI and disk refining). The pretreatments selectively solubilize acetyl groups (> 86%) and lignin (10–63%) while mostly preserving structural carbohydrates in the solid phase. Enzymatic hydrolysis generates hydrolysates of clean sugars (glucose and xylose), with sugar yields increasing up to 81% for glucose and 89% for xylose in response to delignification and mechanical refining. Biochemical methane potential assays reveal specific methane productions of up to 568 NmL CH₄ gVS⁻¹ for alkaline liquor monodigestion and 344 NmL CH₄ gVS⁻¹ for co-digestion with sugarcane vinasse from the conventional (1G) sugarcane ethanol, indicating a strong potential for bioenergy recovery from this process stream. Synergies are identified in integrating 1G ethanol, 2G DMR processing of bagasse, and anaerobic co-digestion of 1G vinasse and 2G DMR alkaline liquor. This technology enables sugarcane biorefineries to enhance the co-production of ethanol, methane, and concentrated streams of CO 2 .

09 BIOMASS FUELS↗

Intense deep-red zero phonon line emission of Mn 4+ in double perovskite La 4 Ti 3 O 12

Phosphors that emit in the deep-red spectral region are critical for plant cultivation light-emitting diodes. In this work, ultrabroadband deep-red luminescence of Mn 4+ in La 4 Ti 3 O 12 was studied, which showed intense zero phonon line emission. The double-perovskite structural La 4 Ti 3 O 12 simultaneously contains two Ti 4+ sites forming slightly- and highly-distorted TiO 6 octahedra, respectively. The influence of octahedral distortion on the Mn 4+ emission energy in the two distinct Ti 4+ sites was studied both experimentally and theoretically. The spectral measurements indicated that Mn 4+ in La 4 Ti 3 O 12 showed intense zero phonon line emission (ZPL) at deep-red 710–740 nm under excitation of 400 nm charging the O 2- → Mn 4+ charge transfer transition. The splitting of the ZPL of the Mn 4+ 2 E g → 4 A 2g transition as well as the intensity of ZPL relative to the vibronic phonon sideband emissions were found to be greatly influenced by the degree of octahedral distortion. The crystal-field strength and Racah parameters of Mn4+ in each Ti4+ site were also estimated. The Mn 4+ 2 E g → 4 A 2g luminescence exhibited severe thermal quenching, which was explained by the low-lying 4 T 2g level and charge-transfer state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Front-End Engineering Design for Piperazine with the Advanced Stripper

This Department of Energy (DOE) funded project was executed with the goal of preparing a Front-End Engineering Design (FEED) for the capture and compression of 90% of the CO2 that would normally be emitted from an existing natural gas combined cycle (NGCC) plant. The FEED focused on the application of the piperazine advanced stripper (PZAS) process at Mustang Station of the Golden Spread Electric Cooperative (GSEC), which consists of two gas turbines with common heat recovery steam generator (HRSG). The University of Texas at Austin (UT) served as the prime contractor, and subcontracted AECOM Technical Services and Trimeric Corporation to support FEED development. This project team has worked together to advance PZAS for more than a decade. ExxonMobil, Chevron, and Total provided project co-funding. The objectives of this work included: 1. To advance engineering design such that a comprehensive estimate for the total installed cost of a full-scale PZAS CO2 Capture Plant with CO2 compression can be developed on an existing NGCC power plant. a. These detailed costs can also be used to qualify PZAS and other related second generation (2G) amine scrubbing processes for use on cogeneration facilities in refineries and chemical plants that use gas turbines with HRSGs to produce steam. b. These detailed costs will help qualify 2G amine scrubbing for use on NGCC power plants and establish a more accurate baseline cost to be used as a target by other capture technologies. 2. To provide cost details to be used in the economic optimization of the process features of PZAS and other 2G amine scrubbing processes. 3. To provide DOE with a more detailed understanding of carbon capture costs in a commercial application, enabling DOE to better design its R&D program to improve the economics for carbon capture. 4. To provide the host site and cost share partners with the information necessary to determine whether a commercial project to capture and use CO2 for enhanced oil recovery (EOR) or for sequestration can be justified (when accounting for the 45Q tax credit). A key component of the FEED is the estimated total installed cost, which provides a basis for the likely capital investment necessary to implement the PZAS carbon capture process at this location and scale. In combination with the included economic analysis, which accounts for potential revenue from the produced CO2, potential avenues to profitability are explored. The major findings of the FEED are as follows: The Mustang Station PZAS CO2 Capture Plant estimated total project cost of $698 MM of which $384 MM was direct costs. The annual operating costs were $32.6 MM. The total investment for a PZAS facility at Mustang Station is $725 MM. This estimate includes owner’s cost of $25 million and a contingency of $110 MM. • The study estimated the CO2 capture plant at Mustang Station would generate CO2 at $110/tonne for EOR, assuming a 12% IRR (internal rate of return) and an 85% capacity factor. For CO2 storage, the same case would achieve a 12% IRR at about $114/tonne. At a capacity factor of 52%, the storage and EOR cases would break even when carbon is priced ~$150/tonne. The economic analysis determined that the capacity factor and utility pricing, among other variable factors, had a significant effect on the economics and will need additional studied. • The energy penalty of the PZAS plant would be about 46 MW in connected power and 35 MW in operating load. The natural gas requirement (for the Gas Boiler package) would be about 354 MMBTU/hr. • The FEED revealed no major risks in process maturity. However, some areas were outlined for further engineering during detailed design, which included the Gas Boiler system, general arrangement and site layout, air coolers, schedule development, and optimization of the process for higher CO2 removal. • If PZAS were to be implemented at another host site, additional opportunities for cost reduction for would include cost reduction through use of cooling water and steam extraction.

03 NATURAL GAS↗

Angle-resolved polarized Raman spectroscopy study of phosphorene nanoribbons

We present a systematic angle-resolved polarized Raman spectroscopy (ARPRS) study of black phosphorus (BP) nanostructures formed via electrochemical sodium- and lithium-ion intercalation. Sodium intercalation leads to bundles of densely packed, highly uniform phosphorene nanoribbons (PNRs) separated by parallel amorphous channels, whereas lithium intercalation results in shorter, irregular nanoribbon-like segments with lower aspect ratios. In both cases, six additional Raman peaks (P1–P6) appear alongside the three primary Raman-active modes of BP (A$^{1}_{g}$, B 2g , and A$^{2}_{g}$). These peaks are attributed to the amorphous regions, as confirmed by their isotropic angular dependence in ARPRS measurements. The three BP modes show pronounced angular variations that differ significantly between the two intercalated samples. In sodium-intercalated BP, A$^{1}_{g}$ and A$^{2}_{g}$ modes retain a dumbbell-like angular dependence under parallel polarization with enhanced anisotropy and reduced symmetry under crossed polarization. At the same time, the B 2g mode transitions from four-lobed (cloverleaf) polar plot to a butterfly-like one. In contrast, lithium-intercalated BP exhibits weaker anisotropy and less distinct angular polar plots for all three modes. These differences reflect the sensitivity of phonon behavior to underlying nanostructure morphology. The vibrational frequencies density of states (FDOS) calculations attribute the B 2g mode transformation to phonon band folding and mode mixing in PNRs. This study demonstrates the power of ARPRS in probing phonon-structure relationships and highlights the influence of edge geometry and quantum confinement on phonon dispersion in PNRs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗