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At least 1,693 records · Page 94
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Phase stability and magnetic and electronic properties of a spark plasma sintered CoFe – P soft magnetic alloy

More efficient power conversion devices are able to transmit greater electrical power across larger distances to satisfy growing global electrical needs. A critical requirement to achieve more efficient power conversion are the soft magnetic materials used as core materials in transformers, inductors, and motors. To that effect it is well known that the use of non-equilibrium microstructures, which are, for example, nanocrystalline or consist of single phase solid solutions, can yield high saturation magnetic polarization and high electrical resistivity necessary for more efficient soft magnetic materials. In this work, we synthesized CoFe – P soft magnetic alloys containing nanocrystalline, single phase solid solution microstructures and studied the effect of a secondary intermetallic phase on the saturation magnetic polarization and electrical resistivity of the consolidated alloy. Single phase solid solution CoFe – P alloys were prepared through mechanically alloying metal powders and phase decomposition was observed after subsequent consolidation via spark plasma sintering (SPS) at various temperatures. The secondary intermetallic phase was identified as the orthorhombic (Co x Fe 1-x ) 2 P phase and the magnetic properties of the (Co x Fe 1-x ) 2 P intermetallic phase were found to be detrimental to the soft magnetic properties of the targeted CoFe – P alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Reduced dislocation density in Ga x In 1–x P compositionally graded buffer layers through engineered glide plane switch

In this work we develop control over dislocation glide dynamics in Ga x In 1-x P compositionally graded buffer layers (CGBs) through control of CuPt ordering on the group-III sublattice. The ordered structure is metastable in the bulk, so any glissile dislocation that disrupts the ordered pattern will release stored energy, and experience an increased glide force. Here we show how this connection between atomic ordering and dislocation glide force can be exploited to control the threading dislocation density (TDD) in Ga x In 1-x P CGBs. When ordered Ga x In 1-x P is graded from the GaAs lattice constant to InP, the order parameter ..eta.. decreases as x decreases, and dislocation glide switches from one set of glide planes to the other. This glide plane switch (GPS) is accompanied by the nucleation of dislocations on the new glide plane, which typically leads to increased TDD. We develop control of the GPS position within a Ga x In 1-x P CGB through manipulation of deposition temperature, surfactant concentration, and strain-grading rate. We demonstrate a two-stage Ga x In 1-x P CGB from GaAs to InP with sufficiently low TDD for high performance devices, such as the 4-junction inverted metamorphic multi-junction solar cell, achieved through careful control the GPS position. Here, experimental results are analyzed within the context of a model that considers the force balance on dislocations on the two competing glide planes as a function of the degree of ordering.

14 SOLAR ENERGY↗
DOE OSTI2015

Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13}: A new telluro-phosphate with S=1/2 Heisenberg chain

A new telluro-phosphate compound Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13} with S=1/2 Heisenberg chain has been successfully synthesized by solid state reaction and grown by flux method. Single crystal X-ray diffraction reveals that Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13} crystallizes into a monoclinic space group C2/c and cell parameters of a=17.647(3) Å, b=7.255(2) Å, c=9.191(2) Å and β=100.16 (3)°. In the structure of Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13}, one dimensional [CuTePO{sub 7}]{sup 3−} chains are formed by tetrahedral PO{sub 4} and trigonal bi-pyramidal TeO{sub 4} joining square planar CuO{sub 4} groups. Those [CuTePO{sub 7}]{sup 3−} chains are inter-connected by sharing one oxygen atom from the TeO{sub 4} group to form two dimensional layers. Magnetic susceptibility and specific heat measurements confirm that the title compound is a model one dimensional Heisenberg antiferromagnetic chain system. - Graphical abstract: Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13}, containing (CuTePO{sub 7}){sup 3−} chains formed by PO{sub 4} and TeO{sub 4} joining CuO{sub 4} groups, shows typical 1D Heisenberg antiferromagnetic chain model behavior as confirmed by magnetic measurements. - Highlights: • New telluro-phosphate Ba{sub 2}Cu{sub 2}Te{sub 2}P{sub 2}O{sub 13} has been grown. • It features layered structure composed of [CuTePO{sub 7}]{sup 3−} chains and TeO{sub 4} groups. • It shows the Heisenberg antiferromagnetic chain behavior. • It is transparent in the range of 1000–2500 nm with a UV absorption edge of 393 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Trap assisted space charge conduction in p-NiO/n-ZnO heterojunction diode

Highlights: • p-NiO/n-ZnO heterojunction diode with enhanced junction parameters has been prepared. • Temperature dependent I–V throw insight into the involved conduction mechanism. • SCLC with exponential trap distribution was found to be the dominant mechanism. • C–V measurement at different frequencies support the presence of traps. - Abstract: The development of short-wavelength p–n junction is essentially important for the realization of transparent electronics for next-generation optoelectronic devices. In the present work, a p–n heterojunction diode based on p-NiO/n-ZnO has been prepared under the optimised growth conditions exhibiting improved electrical and junction parameters. The fabricated heterojunction gives typical current–voltage (I–V) characteristics with good rectifying behaviour (rectification ratio ≈ 10{sup 4} at 2 V). The temperature dependent current–voltage characteristics of heterojunction diode have been studied and origin of conduction mechanism is identified. The space-charge limited conduction with exponential trap distribution having deep level trap is found to be the dominant conduction mechanism in the fabricated p–n heterojunction diode. The conduction and valence band discontinuities for NiO/ZnO heterostructure have been determined from the capacitance–voltage (C–V) measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Erbium-doped borosilicate glasses containing various amounts of P{sub 2}O{sub 5} and Al{sub 2}O{sub 3}: Influence of the silica content on the structure and thermal, physical, optical and luminescence properties

Highlights: • Er{sup 3+} doped borosilicate glasses were processed with different compositions and characterizations. • An increase in the SiO{sub 2} content leads to a silicate-rich environment around the Er{sup 3+} site. • An increase in the SiO{sub 2} content decreases the Er{sup 3+} absorption cross-section at 980 nm. • Glasses with 60 mol% of SiO{sub 2} exhibit a stronger emission intensity at 1530 nm than glasses with x = 50. • Highest 1.5 μm emission intensity was achieved for the Al and P containing glass with 60 mol% of SiO{sub 2}. - Abstract: The influence of the silica content on several properties of Er-doped borosilicate glasses in the presence of various amounts of P{sub 2}O{sub 5} and Al{sub 2}O{sub 3} has been investigated. The introduction of P{sub 2}O{sub 5} and/or Al{sub 2}O{sub 3} are responsible for structural modifications in the glass network through a charge-compensation mechanism related to the formation of negatively-charged PO{sub 4} and AlO{sub 4} groups or through the formation of AlPO{sub 4}-like structural units. In this paper, we show that an increase in the SiO{sub 2} content leads to a silicate-rich environment around the Er{sup 3+} site, resulting in an increased dependence of the Er{sup 3+} ions optical and luminescence properties on the P{sub 2}O{sub 5} and/or Al{sub 2}O{sub 3} concentration. The highest emission intensity at 1.5 μm was achieved for the glass with an equal proportion of P and Al in the glass system with 60 mol% of SiO{sub 2}.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Kinematic and dynamical origins of mean-p T fluctuations in heavy-ion collisions

Event-by-event fluctuations of the mean transverse momentum (mean-p T ) provide a sensitive probe of collective dynamics beyond single-particle spectra and anisotropic flow. We present a systematic study of mean-p T fluctuation observables using a Bayesian-calibrated multistage hydrodynamic framework, including quantitative comparisons to RHIC measurements and model-based investigations of beam-energy and kinematic-acceptance effects. The experimental definitions employed by the STAR and ALICE Collaborations are implemented explicitly and found to yield consistent results within controlled limits. We study the centrality and beam-energy dependence of the observable, its sensitivity to key soft-sector ingredients, and the impact of the kinematic p T acceptance. By introducing scaled-p T cuts, we demonstrate that a part of the apparent energy dependence arises from kinematic projection effects, while the remaining trends reflect genuine collective dynamics. Our results establish mean-p T fluctuations as a nontrivial and independent validation of calibrated hydrodynamic descriptions of the quark–gluon plasma.

Event-by-event correlations↗
DOE OSTI2018

Chemical Bonding and Transport Properties in Clathrates-I with Cu–Zn–P Frameworks

Here quaternary clathrate-I phases with an overall composition of Ba 8 M 16+y P 30-y (M = Cu,Zn) exhibit complex structural chemistry. Characterization of the electronic structures and chemical bonding using quantum-chemical calculations and 31 P solid state NMR spectroscopy demonstrated that the Cu–Zn–P framework is flexible and able to accommodate up to six Zn atoms per formula unit via bonding rearrangements, such as partial Zn/P substitution and the formation of Cu–Zn bonds. Such perturbations of the framework’s bonding affect the thermal and charge transport properties. The overall thermoelectric figure-of-merit, ZT , of Ba 8 Cu 14 Zn 2 P 30 is 0.62 at 800 K, which is 9 times higher than the thermoelectric performance of the ternary parent phase Ba 8 Cu 16 P 30 . Through a combination of inelastic neutron scattering and single crystal X-ray diffraction experiments at 10 K, low-energy rattling of the Ba guest atoms inside the large tetrakaidecahedral cages are shown to be the reason for the low thermal conductivities observed for the studied clathrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Theoretical Study of the Phenoxy Radical Recombination with the O( 3 P) Atom, Phenyl plus Molecular Oxygen Revisited

Quantum chemical calculations of the C 6 H 5 O 2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O( 3 P) and phenyl + O 2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multi-reference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O( 3 P) reaction. Stationary points on the C 6 H 5 O 2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multi-reference character of the wave function. Conventional, variational, and variable reaction coordinate transition state theories were employed in Rice-Ramsperger-Kassel-Marcus Master Equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the main bimolecular product channels of the phenoxy + O( 3 P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO, and, at high temperatures, also phenyl + O 2 . The main bimolecular product channels of the phenyl + O 2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures, and phenoxy + O( 3 P) at higher temperatures. Both for the phenoxy + O( 3 P) and phenyl + O 2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Multiplexed photoionization mass spectrometry investigation of the O( 3 P) + propyne reaction

Here, the reaction of O( 3 P) + propyne (C 3 H 4 ) was investigated at 298 K and 4 Torr using time-resolved multiplexed photoionization mass spectrometry and a synchrotron-generated tunable vacuum ultraviolet light source. The time-resolved mass spectra of the observed products suggest five major channels under our conditions: C 2 H 3 + HCO, CH 3 + HCCO, H + CH 3 CCO, C 2 H 4 + CO, and C 2 H 2 + H 2 + CO. The relative branching ratios for these channels were found to be 1.00, (0.35 ± 0.11), (0.18 ± 0.10), (0.73 ± 0.27), and (1.31 ± 0.62). In addition, we observed signals consistent with minor production of C 3 H 3 + OH and H 2 + CH 2 CCO, although we cannot conclusively assign them as direct product channels from O( 3 P) + propyne. The direct abstraction mechanism plays only a minor role (≤1%), and we estimate that O( 3 P) addition to the central carbon of propyne accounts for 10% of products, with addition to the terminal carbon accounting for the remaining 89%. The isotopologues observed in experiments using d1-propyne (CH 3 CCD) and analysis of product branching in light of previously computed stationary points on the singlet and triplet potential energy surfaces (PESs) relevant to O( 3 P) + propyne suggest that, under our conditions, (84 ± 14)% of the observed product channels from O( 3 P) + propyne result from intersystem crossing from the initial triplet PES to the lower-lying singlet PES.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Calorimetric Study of Mixed Phosphates Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ) to Evaluate the Electrochemical Trends

Mixed polyanionic compounds have been studied extensively as viable cathode materials for sodium-ion batteries. Mixed phosphates, Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ), provide a low barrier for Na-ion diffusion, being advantageous in comparison to phosphates and pyrophosphates. The reported order of sodium extraction is ambiguous and remains unclear. Despite being structurally similar, electrochemical performance differs for all four analogues with different degrees of (de)sodiation, according to the transition element present. High-temperature oxide melt solution calorimetry has been used to establish the relation between thermodynamic phase stability and observed capacity for this series of mixed phosphates. Thermodynamic phase stability largely depends on the kind of structure, type of bonding, and size of the cations present. So, according to our results, the thermodynamic phase stability follows the order Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 > Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 > Na 4 Co 3 (PO 4 ) 2 P 2 O 7 > Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 . The thermodynamic studies serve as guidelines for the selection of compositions with the potential for fabricating advanced cathode materials with maximum performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Photoelectron Spectroscopic Determination of the Interfacial Energetics of Metal Oxide Protection Layers on p-InP Photocathodes

The interfacial energetics between p-type InP and a series of metal oxides, including TiO 2 , Nb 2 O 5 , Ta 2 O 5 , and HfO 2 , were evaluated using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and optical absorption spectroscopy. The energy of the conduction-band minimum ( E cb ) of TiO 2 and Nb 2 O 5 was more negative (i.e., further from the vacuum level) than the conduction-band minimum at the surface of InP ( E cb,s ), whereas E cb for Ta 2 O 5 and HfO 2 was more positive than E cb,s for InP. The data are consistent with the electrochemical behavior of p-InP coated with various metal oxide candidate protection layers, with TiO 2 and Nb 2 O 5 facilitating interfacial transfer of photogenerated minority-carrier electrons in p-InP photocathodes, and Ta 2 O 5 and HfO 2 blocking photogenerated electrons in p-InP from readily transferring across the oxide-coated photocathodes. The energy of the valence-band maximum ( E vb ) for all of the oxides was much more negative than E vb,s for InP, consistent with observations that these protection layers effectively block hole transport and consequently suppress oxidative degradation of the underlying p-InP photocathodes.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2018

Rapid Microwave Preparation and Composition Tuning of the High-Performance Magnetocalorics (Mn,Fe) 2 (P,Si)

Rapid preparation utilizing assisted microwave heating permits significantly shorter preparation times for magnetocaloric compounds in the (Mn,Fe) 2 (P,Si) family, specifically samples of (Mn,Fe) 2–δ P 0.5 Si 0.5 with starting compositions of δ = 0, 0.06, and 0.12. To fully understand the effects of processing and composition changes on structure and properties, these materials are characterized using synchrotron powder diffraction, neutron powder diffraction, electron microprobe analysis (EMPA), X-ray fluorescence (XRF), and magnetic measurements. The diffraction analysis reveals that increasing δ results in decreasing amounts of the common Heusler (Mn,Fe) 3 Si secondary phase. EMPA shows (Mn,Fe) 2 (P,Si) in all three samples to be Mn and P rich, whereas XRF demonstrates that the bulk material is Mn rich yet P deficient. Increasing δ brings the Mn/Fe and P/Si ratios closer to their starting values. Measurements of magnetic properties show an increase in saturation magnetization and ordering temperature with increasing δ, consistent with the increase in Fe and Si contents. Increasing δ also results in a decrease in thermal hysteresis and an increase in magnetic entropy change. We note the latter reach values close to what have been previously reported on samples that take much longer to prepare.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Simultaneously Improved Efficiency and Stability in All-Polymer Solar Cells by a P–i–N Architecture

All-polymer organic solar cells offer exceptional stability. Unfortunately, the use of bulk heterojunction (BHJ) structure has the intrinsic challenge to control the side-chain entanglement and backbone orientation to achieve sophisticated phase separation in all-polymer blends. Here, we revealed that the P-i-N structure can outperform the BHJ ones with a nearly 50% efficiency improvement, reaching a power conversion efficiency approaching 10%. This P-i-N structure can also provide an enhanced internal electric field and remarkably stable morphology under harsh thermal stress. We have further demonstrated generality of the P-i-N structure in several other all-polymer systems. Considering the adjustable polymer molecular weight and solubility, the P-i-N device structure can be more beneficial for all-polymer systems. With the design of more crystalline polymers, the antiquated P-i-N structure can further show its strength in all-polymer systems by simplified morphology control and improved carrier extraction, becoming a more favorite device structure than the dominant BHJ structure.

14 SOLAR ENERGY↗
DOE OSTI2021

Single Iridium Atom Doped Ni 2 P Catalyst for Optimal Oxygen Evolution

Single-atom catalysts (SACs) with 100% active sites have excellent prospects for application in the oxygen evolution reaction (OER). However, further enhancement of the catalytic activity for OER is quite challenging, particularly for the development of stable SACs with overpotentials <180 mV. Here, we report an iridium single atom on Ni 2 P catalyst (Ir SA -Ni 2 P) with a record low overpotential of 149 mV at a current density of 10 mA·cm –2 in 1.0 M KOH. The Ir SA -Ni 2 P catalyst delivers a current density up to ∼28-fold higher than that of the widely used IrO 2 at 1.53 V vs RHE. Both the experimental results and computational simulations indicate that Ir single atoms preferentially occupy Ni sites on the top surface. The reconstructed Ir–O–P/Ni–O–P bonding environment plays a vital role for optimal adsorption and desorption of the OER intermediate species, which leads to marked enhancement of the OER activity. Additionally, the dynamic “top-down” evolution of the specific structure of the Ni@Ir particles is responsible for the robust single-atom structure and, thus, the stability property. In conclusion, this Ir SA -Ni 2 P catalyst offers novel prospects for simplifying decoration strategies and further enhancing OER performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

p-Type BiVO 4 for Solar O 2 Reduction to H 2 O 2

Photoelectrochemical cells (PECs) can directly utilize solar energy to drive chemical reactions to produce fuels and chemicals. Oxide-based photoelectrodes in general exhibit enhanced stability against photocorrosion, which is a critical advantage for building a sustainable PEC. However, most oxide-based semiconductors are n-type, and p-type oxides that can be used as photocathodes are limited. In this study, we report the synthesis, characterization, and application of p-type BiVO 4 with a monoclinic scheelite (ms) structure. ms-BiVO 4 is inherently n-type, and it has been investigated only as a photoanode to date. In this study, we prepared p-type ms-BiVO 4 (bandgap of 2.4 eV) via atomic doping of Ca 2+ at the Bi 3+ site under an O 2 -rich environment and examined its performance as a photocathode. We then demonstrated that the Ca-doped ms-BiVO 4 photocathode can be used for solar O 2 reduction to H 2 O 2 when coupled with appropriate catalysts. Our computational investigation using hybrid density functional theory revealed that holes are stable as polarons in ms-BiVO 4 and have a low self-trapping energy, that may lead to free carriers in the valence band at finite temperature. Our calculations also show that Ca is an effective shallow acceptor dopant with low formation energy and thermal ionization energy leading to p-type conductivity. In conclusion, our joint experimental and computational results provide critical insights into the design of p-type ms-BiVO 4 , enabling its use as a polaronic oxide photocathode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation

Achieving stable operation of photoanodes used as components of solar water splitting devices is essential to realizing the promise of this renewable energy technology. It is demonstrated that p-type transparent conducting oxides (p-TCOs) can function both as a selective hole contact and corrosion protection layer for photoanodes used in light-driven water oxidation. Using NiCo 2 O 4 as the p-TCO and n-type Si as a prototypical light absorber, a rectifying heterojunction capable of light driven water oxidation was created. By placing the charge separating junction in the Si using a np + structure and by incorporating a highly active heterogeneous Ni-Fe oxygen evolution catalyst, efficient light-driven water oxidation can be achieved. In this structure, oxygen evolution under AM 1.5 G illumination occurs at 0.95 V vs RHE, and the current density at the reversible potential for water oxidation (1.23 V vs RHE) is >25 mA cm -2 . Stable operation was confirmed by observing a constant current density over 72 h and by sensitive measurements of corrosion products in the electrolyte. In situ Raman spectroscopy was employed to investigate structural transformation of NiCo 2 O 4 during electrochemical oxidation. The interface among the light absorber and p-TCO is crucial to produce selective hole conduction to the surface under illumination. For example, annealing to produce more crystalline NiCo 2 O 4 produces only small changes in its hole conductivity, while a thicker SiO x layer is formed at the n-Si/p-NiCo 2 O 4 interface, greatly reducing the PEC performance. The generality of the p-TCO protection approach is demonstrated by multihour, stable, water oxidation with n-InP/p-NiCo 2 O 4 heterojunction photoanodes.

Chen, Le↗
DOE OSTI2018

Seamless lateral graphene p–n junctions formed by selective in situ doping for high-performance photodetectors

Lateral graphene p–n junctions are important since they constitute the core components in a variety of electronic/photonic systems. However, formation of lateral graphene p–n junctions with a controllable doping levels is still a great challenge due to the monolayer feature of graphene. Herein, by performing selective ion implantation and in situ growth by dynamic chemical vapor deposition, direct formation of seamless lateral graphene p–n junctions with spatial control and tunable doping is demonstrated. Uniform lattice substitution with heteroatoms is achieved in both the boron-doped and nitrogen-doped regions and photoelectrical assessment reveals that the seamless lateral p–n junctions exhibit a distinct photocurrent response under ambient conditions. As ion implantation is a standard technique in microelectronics, our study suggests a simple and effective strategy for mass production of graphene p–n junctions with batch capability and spatial controllability, which can be readily integrated into the production of graphene-based electronics and photonics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pd/C promotes C–H bond activation and oxidation of p -hydroxybenzoate during hydrogenolysis of poplar

Hydrogenolysis of lignin generates a portfolio of products, the yields of which are generally calculated using a subset of phenolic monomers that are dependent on the lignin composition, product distribution, and analytical technique. Some lignins are naturally γ-acylated; poplar lignins, for example, have p-hydroxybenzoate groups on 1–15% of their syringyl subunits. Upon hydrogenolysis, it is generally assumed that the p-hydroxybenzoate is cleaved before the deacylated lignin is depolymerized. Hydrogenolysis of model γ-p-hydroxybenzoylated β-aryl ethers do not, however, produce the deacylated β-aryl ether intermediates, as was previously conjectured; products instead derive from palladium-assisted reactions on the cinnamyl p-hydroxybenzoates resulting in initial β-ether cleavage. The p-hydroxybenzoate moiety itself also undergoes carboxylate-assisted palladium-catalyzed C–H bond activation to form the 2,4-dihydroxybenzoate, that subsequently converts to the 2,4-dihydroxycyclohex-1-enoate. Furthermore, these details underscore previously unrecognized pathways and products that are key to understanding the different hydrogenolysis product distributions from naturally acylated lignins that are prevalent biomass-conversion feedstocks.

09 BIOMASS FUELS↗