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W(CO)6 is Cubic alpha N2-derived structured and crystallizes in the orthorhombic Pnma space group. The structure is zero-dimensional and consists of twenty-four formaldehyde molecules and four tungsten molecules.
The nonionic deep eutectic solvent, formed by lauric acid (LA) and N-methylacetamide (NMA), has been shown to have a heterogeneous molecular structure in which the LA and NMA form nonpolar and polar domains, respectively. Previous vibrational spectroscopy experiments demonstrated that the ability of the LA domains to solvate compounds was limited to long carbon chains, whereas other nonpolar molecules, such as W(CO) 6 , were found to be solvated by both LA and NMA. These experiments were not fully compatible with the previously proposed micelle-like structure of the nonpolar domains of the LA-NMA DES. In this work, the modeling of the DES molecular structure is pursued using classical molecular dynamics simulations. The new classical model reproduces both the SAXS structural factors and the previously experimentally derived interaction map for these LA-NMA DESs. In addition, the simulation also shows that LA-NMA DESs form highly organized LA aggregates that are difficult to disorganize. Further evidence of the correct description provided by the newly derived model is obtained using a moderately polar probe: chloroform-d. Computations using the classical model have a good agreement with the solvation behavior of the probe derived from experiments, in which the location of the probe is found to be mostly within the polar domain of the DES. The computational model also demonstrates that the probe solvation is a consequence of the tightly packed LA structure, which causes nonpolar molecules to be located at the interphase of the DES nonpolar domains.
In this work, we present a relativistic quantum embedding formalism capable of variationally treating relativistic effects, including scalar-relativity and spin–orbit coupling. We extend density functional theory (DFT)-in-DFT projection-based quantum embedding to a relativistic two-component formalism, where the full spin magnetization vector form is retained throughout the embedding treatment. To benchmark various relativistic embedding schemes, spin–orbit splitting of the nominally t 2g valence manifold of W(CO) 6 , exchange coupling of [(H 3 N) 4 Cr(OH) 2 Cr(NH 3 ) 4 ] 4+ , and the dissociation potential curve of WF 6 are investigated. The relativistic embedding formalism introduced in this work is well suited for efficient modeling of open-shell systems containing late transition metal, lanthanide, and actinide molecular complexes.
Here, this paper presents the phase stability and elemental partitioning in a Co-40Ni-10Al-7.5W-10Cr-3Nb-0.06B-0.6C (at.%) superalloy (referred to as 3Nb) after a two-step heat treatment. The resulting microstructure consisted of γ, γ', MC carbides and µ-Co 7 W 6 phase decorating the regions near and at the grain boundaries. Nb preferentially partitioned to the γ'-phase and other elements such as Ni, Cr and W were responsible for the μ-phase formation.
C7Co6W20 crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. there are five inequivalent W sites. In the first W site, W is bonded in a 3-coordinate geometry to three Co and three C atoms. There are two shorter (2.79 Å) and one longer (2.84 Å) W–Co bond lengths. There are two shorter (2.17 Å) and one longer (2.26 Å) W–C bond lengths. In the second W site, W is bonded in a 2-coordinate geometry to three Co and two equivalent C atoms. There are two shorter (2.75 Å) and one longer (2.80 Å) W–Co bond lengths. Both W–C bond lengths are 2.14 Å. In the third W site, W is bonded in a distorted rectangular see-saw-like geometry to two equivalent Co and two equivalent C atoms. Both W–Co bond lengths are 2.62 Å. Both W–C bond lengths are 2.08 Å. In the fourth W site, W is bonded in a distorted rectangular see-saw-like geometry to two equivalent Co and two equivalent C atoms. Both W–Co bond lengths are 2.63 Å. Both W–C bond lengths are 2.09 Å. In the fifth W site, W is bonded in a 6-coordinate geometry to six Co atoms. There are three shorter (2.48 Å) and three longer (2.49 Å) W–Co bond lengths. There are two inequivalent Co sites. In the first Co site, Co is bonded to ten W and two equivalent Co atoms to form distorted CoCo2W10 cuboctahedra that share corners with two equivalent CoCo2W10 cuboctahedra, corners with four equivalent CW6 octahedra, faces with two equivalent CoCo2W10 cuboctahedra, and faces with four equivalent CW6 octahedra. The corner-sharing octahedral tilt angles are 39°. Both Co–Co bond lengths are 2.63 Å. In the second Co site, Co is bonded in a 12-coordinate geometry to ten W and two equivalent Co atoms. Both Co–Co bond lengths are 2.62 Å. There are two inequivalent C sites. In the first C site, C is bonded in a 6-coordinate geometry to six equivalent W atoms. In the second C site, C is bonded to six W atoms to form CW6 octahedra that share corners with two equivalent CoCo2W10 cuboctahedra, corners with six equivalent CW6 octahedra, and faces with two equivalent CoCo2W10 cuboctahedra. The corner-sharing octahedra tilt angles range from 38–50°.
Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.
We report the synthesis, characterization, and solution self-assembly of plenary Nb 6 P 2 W 12 -based transition-metal substituted polyoxometalate, which is obtained by simply adding transition metals (Co 2+ ) into aqueous solution containing cluster [(NbO 2 ) 6 P 2 W 12 O 56 ] 12- , which is obtained by an in situ synthetic method. The incorporation of Co 2+ ions significantly affects the crystal structure, resulting in the formation of a 1D chain-like crystal and the first example of a niobotungstate-based cobalt derivative cluster. The behavior and stability of this cluster in solution are confirmed by time-resolved static light scattering, dynamic light scattering, small-angle X-ray scattering, and electrospray mass spectrometry studies.
W3Te2(CO)6(CO)9 is Magnesium tetraboride-like structured and crystallizes in the tetragonal P4_12_12 space group. The structure is zero-dimensional and consists of thirty-six formaldehyde molecules and four W3Te2(CO)6 clusters. In each W3Te2(CO)6 cluster, there are two inequivalent W+4.67+ sites. In the first W+4.67+ site, W+4.67+ is bonded in a distorted single-bond geometry to one Te2- atom. The W–Te bond length is 2.83 Å. In the second W+4.67+ site, W+4.67+ is bonded in a 2-coordinate geometry to two equivalent Te2- atoms. Both W–Te bond lengths are 3.00 Å. There are three inequivalent C+1.33+ sites. In the first C+1.33+ site, C+1.33+ is bonded in a single-bond geometry to one O2- atom. The C–O bond length is 1.16 Å. In the second C+1.33+ site, C+1.33+ is bonded in a single-bond geometry to one Te2- and one O2- atom. The C–Te bond length is 3.06 Å. The C–O bond length is 1.16 Å. In the third C+1.33+ site, C+1.33+ is bonded in a single-bond geometry to one O2- atom. The C–O bond length is 1.17 Å. Te2- is bonded in a 2-coordinate geometry to two W+4.67+, one C+1.33+, one Te2-, and two O2- atoms. The Te–Te bond length is 2.78 Å. There are one shorter (3.42 Å) and one longer (3.81 Å) Te–O bond lengths. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one C+1.33+ and one Te2- atom. In the second O2- site, O2- is bonded in a single-bond geometry to one C+1.33+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one C+1.33+ and one Te2- atom.
Single crystal superalloy specimens with various crystallographic directions along their axes were tested in compression at room temperature, 650, 760, 870, and 980 deg C. These results are compared with the tensile behavior studied previously. The alloy, Rene N4, was developed for gas turbine engine blades and has the nominal composition 3.7 Al, 4.2 Ti, 4 Ta, 0.5 Nb, 6 W, 1.5 Mo 9 Cr. 7.5 Co, balance Ni, in weight percent. Slip trace analysis showed that primary cube slip occurred even at room temperature for the 111 specimens. With increasing test temperature more orientations exhibited primary cube slip, until at 870 deg C only the 100 and 011 specimens exhibited normal octahedral slip. The yield strength for octahedral slip was numerically analysed using a model proposed by Lall, Chin, and Pope to explain deviations from Schmid's Law in the yielding behavior of a single phase Gamma prime alloy, Ni3(Al, Nb). The Schmid's Law deviations in Rene N4 were found to be largely due to a tension-compression anisotropy. A second effect, which increases trength for orientations away from 001, was found to be small in Rene N4. Analysis of recently published data on the single crystal superalloy PWA 1480 yielded the same result.
Single crystal specimens of a nickel-base superalloy with axes near 001, 011, and -112 were tested in tension at room temperature, 760, and 980 C. The alloy Rene N-4, was developed for gas turbine engine blades and has the nominal composition 3.7 Al, 4.2 Ti, 4 Ta, 0.5 Nb, 6 W, 1.5 Mo, 9 Cr, 7.5 Co, balance Ni, (all in weight percent). Analysis of slip band traces, specimen axis rotation, and dislocation Burgers vectors showed that at 760 and 980 C primary cube slip supplanted normal octahedral slip for the -112 line-oriented specimens. The other two orientations, which have lower resolved shear stresses on the cube system, exhibited octahedral slip at all three temperatures. The critical resolved shear stress is considerably greater on the cube system than on the octahedral system at room temperature. However, at 760 and 980 C the critical resolved shear stresses on the two systems are about the same. While the room temperature and 980 C yield strengths for the two orientations exhibiting octahedral slip could be rationalized on the basis of resolved shear stress, those at 760 C could not. Such violations of Schmid's law have previously been observed in other superalloys and single phase gamma-prime.
We report an order and disorder combined corrosion morphology of dual-phase Ni-based alloy in the passive state. After galvanostatic polarization in the passive region, the surface of the γ(Ni) phase presents amorphous feature while that of the γ′(Ni 3 Al) phase maintains crystalline. The variations in weight percentages of Ni (50.19% → 3.80%), Co (19.24% → 0.65%), Ta (0.85% → 21.19%), and W (5.73% → 43.79%) of γ surface are evident, whereas the composition of γ′ surface is nearly unchanged. The passive film comprises $W^{6+}_{ox}$, $Ta^{5+}_{ox}$, $Cr^{3+}_{ox}$, $Co^{8/3+}_{ox}$, $Ni^{2+}_{hy}$, and $Co^{2+}_{hy}$, and it shows stronger protection effect on the γ phase.
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Hf9W4Co crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Hf sites. In the first Hf site, Hf is bonded in a 1-coordinate geometry to four W and one Co atom. There are a spread of Hf–W bond distances ranging from 2.94–3.09 Å. The Hf–Co bond length is 2.56 Å. In the second Hf site, Hf is bonded in a 2-coordinate geometry to two equivalent W atoms. Both Hf–W bond lengths are 2.89 Å. There are two inequivalent W sites. In the first W site, W is bonded in a 12-coordinate geometry to eight Hf and four W atoms. There are two shorter (2.71 Å) and two longer (2.93 Å) W–W bond lengths. In the second W site, W is bonded to six equivalent Hf and six equivalent W atoms to form face-sharing WHf6W6 cuboctahedra. Co is bonded in a 6-coordinate geometry to six equivalent Hf atoms.
Anomalous lattice expansion of bcc Ta is observed in helium-loaded diamond anvil cell (DAC) experiments near 6 GPa and above 400 K, while co-loaded W, Mo, and Au exhibit normal thermal expansion. The Ta volume expansion increases with temperature, reaching ~14% near 650 K before plateauing, and is largely retained after recovery to ambient conditions. Time-resolved measurements at 500 K reveal progressive expansion over several hours, consistent with gradual, thermally activated He incorporation. The largely retained expansion during subsequent cooling and holding at 400 K indicates that the incorporated He is predominantly kinetically trapped. The data reveal two distinct regimes: below ~550 K, modest and spatially uniform expansion consistent with interstitial He trapping at isolated, randomly distributed vacancies; above ~550 K, He-vacancy cluster growth producing dramatically larger expansion, peak broadening, and a core–shell microstructure revealed by micron-resolution X-ray diffraction mapping. These results demonstrate that He is not always a passive pressure medium in DAC experiments and reveal a previously unrecognized regime of He-mediated lattice modification in Ta, complementing conventional ion-implantation studies relevant to nuclear and fusion structural materials.
Carbon monoxide (CO) and ozone (O3) concentrations have been observed in the Brazilian Amazon region, at a site strongly affected by biomass burning (Cuiaba, 16 deg S, 58 deg W). Time variations are described for the first long-term program of studying the effect of biomass burning on O3 and CO over a complete seasonal cycle, including the seasonal maxima of 1987 and 1988. In order to obtain elements for comparison, an identical observational program was maintained at a site totally outside of the direct influence of biomass burning (Natal, 6 deg S, 35 deg W). The biomass burning contribution to the Cuiaba concentrations of CO and O3 is very large. Diurnal maxima concentrations exceeded 90 ppbv O3 in 1987 and 120 ppbv O3 in 1988, in September. For the wet season, the monthly average ozone concentration in March-April is about 10 ppbv. During the month of maxima, September, the O3 concentration average was 41 ppbv for 1987 and 71 ppbv for 1988. The CO concentrations are about 90 ppbv in the wet season. In September, 460 ppbv and 660 ppbv of CO were observed for 1987 and 1988, respectively. At Natal the seasonal variation is of the order of a factor of 2. During the wet season, the concentrations of CO and O3 at both stations are about the same.
Selective reduction of CO 2 into fuels and chemical feedstocks is highly desirable to reduce our dependence on fossil fuels. Most molecular catalysts afford 2e – reduction products, such as CO or HCO 2 – , as opposed to more reduced products. Here we present an analysis of the thermodynamic limitations for reduction of the CO ligand in the form of a series of isostructural group 6 carbonyl complexes, Cp*M(CO) 3 (P(OMe) 3 ) + (M = Cr, Mo, and W). Additionally, the free energy for stepwise transfer of a hydride (H – ) and a proton (H + ) to the CO ligand, resulting in a hydroxycarbene (CHOH) complex, was measured by equilibration with H – /H + donors and acceptors with known hydricity or acidity. Together, these two reaction steps are equivalent to a net addition of H 2 across the CO ligand. A large and unfavorable free energy for H 2 addition (Δ G ° H2 ) was measured for all three complexes and decreases in the order Cr > Mo > W. The trend for these complexes is opposite to the trend previously reported for group 7 carbonyl complexes, for which Δ G ° H2 decreases moving up the group, Re > Mn. Computational analysis indicates the trends can be described in terms of electrostatic effects, where a low Δ G ° H2 is obtained in complexes that balance the atomic charges of the M–C≡O fragment of the complex. These findings can be used to design metal carbonyl complexes with a more energetically accessible H 2 addition, which will facilitate the development of molecular catalysts for reduction of CO.
W2CoB2 crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. W2+ is bonded in a 6-coordinate geometry to six equivalent B3- atoms. There are four shorter (2.34 Å) and two longer (2.52 Å) W–B bond lengths. Co2+ is bonded in a square co-planar geometry to four equivalent B3- atoms. All Co–B bond lengths are 2.09 Å. B3- is bonded in a 9-coordinate geometry to six equivalent W2+, two equivalent Co2+, and one B3- atom. The B–B bond length is 1.88 Å.
We report on the design, development, and testing of our high-power broadband optical modem supporting NASA’s crewed Artemis-2 mission. The O2O modem will be mounted in the crewed Orion module and provide a broadband 505,000 km bi-directional optical link back to earth while en route to the moon. The full-duplex modem consists of a high-power optical transmitter and receiver optimized for serially-concatenated pulse-position modulation (SCPPM). The transmitter is a master-oscillator power-amplifier optical architecture using efficient cladding-pumped amplification in erbium-ytterbium co-doped fiber. The transmitter outputs up to 1 W at ≈1550 nm (limited for eye safety) and supports 6 different user-rates ranging from 20.39 Mb/s to 260.95 Mb/s using PPM16 and PPM32 modulation formats. The optical receiver supports two user-rates: 10.19 Mb/s and 20.39 Mb/s with both rates employing PPM32. The narrowband receiver filtering is optimized to simultaneously accept four separate wavelength channels to mitigate atmospherics through spatial diversity. A configurable interleaver provides additional protection against atmospherics-based signal fading and a powerful soft-decision error correction scheme enables highly sensitive detection. The measured sensitivities at the two bit-rates are -73.8 and -71.8dBm, respectively. The architecture was designed for reliable operation in space, featuring automatic hardware interlocks, pump sparing for the amplifiers, and autonomous operation of all internal hardware and software control loops. The protoflight unit (PFU) was put through rigorous environmental testing which included pyroshock, vibration, electromagnetic interference/compatibility, and thermal-vacuum testing. The modem successfully passed all the environmental screening and has been declared at Technology Readiness Level (TRL) 6.