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Synthesis of High Surface Area VS2 for Nitrogen Reduction

Ammonia synthesis from dinitrogen provides a critical chemical feedstock to agriculture worldwide. The dominant process for ammonia synthesis is the Haber-Bosch process, which is fossil-fuel dependent and energy intensive. The electrochemical nitrogen reduction reaction (NRR) could provide a more environmentally friendly route to industrial ammonia synthesis. We have worked to realize electrochemical NRR by developing transition metal dichalcogenide NRR catalysts. In the first part of this presentation, a VS2-based NRR electrocatalyst, which has shown promising activity and selectivity, will be presented. The synthesis of this VS2-based catalyst is straightforward and results in few-layer VS2 or VSx, (x < 2) nanoflakes. Additionally, the proposed mechanism of NRR on VS2 will be discussed, and we will discuss DFT simulation of NRR on VS2 and MoS2 as well as planned in-situ Raman experiments to probe this mechanism. In the second part of this presentation, we will share several lessons learned during our early NRR research including important points of electrochemical cell design and experimental controls to reduce environmental ammonia contamination of experiments. Finally, we will address areas of opportunity for electrochemical NRR.

dichalcogenide↗

Materials Data on VS2 by Materials Project

VS2 is trigonal omega-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two VS2 sheets oriented in the (0, 0, 1) direction. V4+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.36 Å. S2- is bonded in a distorted T-shaped geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 is trigonal omega-like structured and crystallizes in the triclinic P-1 space group. The structure is two-dimensional and consists of one VS2 sheet oriented in the (0, 0, 1) direction. V4+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.35 Å. S2- is bonded in a distorted T-shaped geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 crystallizes in the monoclinic P2/m space group. The structure is one-dimensional and consists of one VS2 ribbon oriented in the (1, 0, 0) direction. V4+ is bonded in a square co-planar geometry to four equivalent S2- atoms. All V–S bond lengths are 2.25 Å. S2- is bonded in an L-shaped geometry to two equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three VS2 sheets oriented in the (0, 0, 1) direction. V4+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.36 Å. S2- is bonded in a 3-coordinate geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 is Molybdenite structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is two-dimensional and consists of two VS2 sheets oriented in the (0, 0, 1) direction. V4+ is bonded to six equivalent S2- atoms to form distorted edge-sharing VS6 pentagonal pyramids. All V–S bond lengths are 2.37 Å. S2- is bonded in a 3-coordinate geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 is trigonal omega-like structured and crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of three VS2 sheets oriented in the (0, 0, 1) direction. V4+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.36 Å. S2- is bonded in a distorted T-shaped geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 crystallizes in the triclinic P1 space group. The structure is two-dimensional and consists of one vanadium molecule and two S sheets oriented in the (0, 0, 1) direction. In each S sheet, S2- is bonded in a hexagonal planar geometry to six equivalent S2- atoms. There are a spread of S–S bond distances ranging from 2.55–2.60 Å.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 crystallizes in the triclinic P1 space group. The structure is two-dimensional and consists of one vanadium dust molecule and two S sheets oriented in the (0, 0, 1) direction. In each S sheet, S2- is bonded in a square co-planar geometry to four equivalent S2- atoms. There are two shorter (2.30 Å) and two longer (2.39 Å) S–S bond lengths.

36 MATERIALS SCIENCE↗

Materials Data on Na(VS2)2 by Materials Project

Na(VS2)2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. Na1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Na–S bond distances ranging from 2.86–2.93 Å. There are two inequivalent V+3.50+ sites. In the first V+3.50+ site, V+3.50+ is bonded to six S2- atoms to form edge-sharing VS6 octahedra. There are a spread of V–S bond distances ranging from 2.34–2.48 Å. In the second V+3.50+ site, V+3.50+ is bonded to six S2- atoms to form edge-sharing VS6 octahedra. There are a spread of V–S bond distances ranging from 2.32–2.48 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Na1+ and three V+3.50+ atoms to form a mixture of distorted edge and corner-sharing SNa2V3 square pyramids. In the second S2- site, S2- is bonded to two equivalent Na1+ and three V+3.50+ atoms to form a mixture of distorted edge and corner-sharing SNa2V3 trigonal bipyramids. In the third S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to one Na1+ and three V+3.50+ atoms. In the fourth S2- site, S2- is bonded in a distorted rectangular see-saw-like geometry to one Na1+ and three V+3.50+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 is trigonal omega-like structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. V4+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.36 Å. S2- is bonded in a distorted T-shaped geometry to three equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ca(VS2)4 by Materials Project

Ca(VS2)4 is beta indium sulfide-derived structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Ca2+ is bonded in a 6-coordinate geometry to six equivalent S2- atoms. All Ca–S bond lengths are 2.79 Å. There are two inequivalent V+3.50+ sites. In the first V+3.50+ site, V+3.50+ is bonded to six S2- atoms to form edge-sharing VS6 octahedra. There are two shorter (2.37 Å) and four longer (2.39 Å) V–S bond lengths. In the second V+3.50+ site, V+3.50+ is bonded to six equivalent S2- atoms to form edge-sharing VS6 octahedra. All V–S bond lengths are 2.37 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded in a rectangular see-saw-like geometry to one Ca2+ and three V+3.50+ atoms. In the second S2- site, S2- is bonded in a distorted T-shaped geometry to three equivalent V+3.50+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on VS2 by Materials Project

VS2 crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. V4+ is bonded to four equivalent S2- atoms to form corner-sharing VS4 tetrahedra. All V–S bond lengths are 2.22 Å. S2- is bonded in a bent 120 degrees geometry to two equivalent V4+ atoms.

36 MATERIALS SCIENCE↗

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Moderate temperature sodium cells. I - Transition metal disulfide cathodes

TiS2, VS2, and Nb(1.1)S2 transition metal disulfides were evaluated as cathode materials for a moderate temperature rechargeable Na cell operating at 130 C. The 1st discharge of TiS2 results in a capacity of 0.85 eq/mole; approximately half of the Na in the 1st phase spanning the Na range from zero to 0.30 and almost all the Na in the 2nd phase spanning the 0.37 to 0.80 range are rechargeable. VS2 intercalates up to one mole of Na/mole of VS2 in the 1st discharge; the resulting Na(x)VS2 ternary consists of 3 phases in the 3 ranges of Na from zero to 1. Niobium disulfide undergoes a phase change in the 1st discharge; the average rechargeable capacity in extended cycling of this cathode is 0.50 eq/mole.

Abraham, K. M.↗

Moderate temperature rechargeable sodium batteries

Cells utilizing the organic electrolyte, NaI in triglyme, operated at approx. 130 C with Na(+) - intercalating cathodes. However, their rate and stability were inadequate. NaAlCl4 was found to be a highly useful electrolyte for cell operation at 165-190 C. Na(+) intercalating chalcogenides reacted with NaAlCl4 during cycling to form stable phases. Thus, VS2 became essentially VS2Cl, with reversible capacity of approx 2.8 e(-)/V, and a mid-discharge voltage of approx 2.5V and 100 deep discharge cycles were readily achieved. A positive electrode consisting of VCl3 and S plus NaAlCl4 was subjected to deep-discharge cycles 300 times and it demonstrated identity with the in-situ-formed BSxCly cathode. NiS2 and NiS which are not Na(+)-intercalating structures formed highly reversible electrodes in NaAlCl4. The indicated discharge mechanism implies a theoretical capacity 4e(-)/Ni for NiS2 and 2e(-)/Ni for NiS. The mid-discharge potentials are, respectively, 2.4V and 2.1V. A Na/NiS2 cell cycling at a C/5 rate has exceeded 500 deep discharge cycles with 2.5e(-)/Ni average utilization. A 4 A-hr nominal capacity prototype Na/NiS2 cell was tested at 190 C. It was voluntarily terminated after 80 cycles. Further development, particularly of cathode structure and hardware should produce a battery capable of at least 50-W-hr/lb and more than 1000 cycles.

Abraham, K. M.↗