Coordination Structure Modulation in Group-VIB Metal Doped Ag3PO4 Augments Active Site Density for Electrocatalytic Conversion of N2 to NH3.

Doping is considered a promising material engineering strategy in electrochemical nitrogen reduction reaction (NRR), provided the role of the active site is rightly identified. This work concerns the doping of group VIB metal in Ag3PO4 to enhance the active site density, accompanied by d-p orbital mixing at the active site/N2 interface. Doping induces compressive strain in the Ag3PO4 lattice and inherently accompanies vacancy generation, the latter is quantified with positron annihilation lifetime studies (PALS). This eventually alters the metal d-electronic states relative to Fermi level and manipulate the active sites for NRR resulting into side-on N2 adsorption at the interface. The charge density deployment reveals Mo as the most efficient dopant, attaining a minimum NRR overpotential, as confirmed by the detailed kinetic study with the rotating ring disk electrode (RRDE) technique. In fact, the Pt ring of RRDE fails to detect N2H4, which is formed as a stable intermediate on the electrode surface, as identified from in-situ attenuated total reflectance-infrared (ATR-IR) spectroscopy. This advocates the complete conversion of N2 to NH3 on Mo/Ag3PO4-10 and the so-formed oxygen vacancies formed during doping act as proton scavengers suppressing hydrogen evolution reaction resulting into a Faradaic efficiency of 54.8% for NRR.

Chemical bonding and electronic properties along Group 13 metal oxides.

CONTEXT: The present work provides a systematic theoretical analysis of the nature of the chemical bond in Al2O3, Ga2O3, and In2O3 group 13 cubic crystal structure metal oxides. The influence of the functional in the resulting band gap is assessed. The topological analysis of the electron density provides unambiguous information about the degree of ionicity along the group which is linearly correlated with the band gap values and with the cost of forming a single oxygen vacancy. Overall, this study offers a comprehensive insight into the electronic structure of metal oxides and their interrelations. This will help researchers to harness information effectively, boosting the development of novel metal oxide catalysts or innovative methodologies for their preparation. METHODS: Periodic density functional theory was used to predict the atomic structure of the materials of interest. Structure optimization was carried out using the PBE functional, using a plane wave basis set and the PAW representation of the atomic cores, using the VASP code. Next, the electronic properties were computed by carrying out single point calculations employing PBE, PBE + U functionals using VASP and also with PBE and the hybrid HSE06 functionals using the FHI-AIMS software. For the hybrid HSE06, the impact of the screening parameter, ω, and mixing parameter, α, on the calculated band gap has also been assessed.

Atomic and Electronic Structures of Co-Doped In2O3 from Experiment and Theory.

The synthesis and properties of stoichiometric, reduced, and Co-doped In2O3 are described in the light of several experimental techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)-visible spectroscopy, porosimetry, and density functional theory (DFT) methods on appropriate models. DFT-based calculations provide an accurate prediction of the atomic and electronic structure of these systems. The computed lattice parameter is linearly correlated with the experimental result in the Co concentration ranging from 1.0 to 5.0%. For higher Co concentrations, the theoretical-experimental analysis of the results indicates that the dopant is likely to be preferentially present at surface sites. The analysis of the electronic structure supports the experimental assignment of Co2+ for the doped material. Experiments and theory find that the presence of Co has a limited effect on the material band gap.

Engineering hydrophobic-aerophilic interfaces to boost N2 diffusion and reduction through functionalization of fluorine in second coordination spheres.

Ammonia is a crucial biochemical raw material for nitrogen containing fertilizers and a hydrogen energy carrier obtained from renewable energy sources. Electrocatalytic ammonia synthesis is a renewable and less-energy intensive way as compared to the conventional Haber-Bosch process. The electrochemical nitrogen reduction reaction (eNRR) is sluggish, primarily due to the deceleration by slow N2 diffusion, giving rise to competitive hydrogen evolution reaction (HER). Herein, we have engineered a catalyst to have hydrophobic and aerophilic nature via fluorinated copper phthalocyanine (F-CuPc) grafted with graphene to form a hybrid electrocatalyst, F-CuPc-G. The chemically functionalized fluorine moieties are present in the second coordination sphere, where it forms a three-phase interface. The hydrophobic layer of the catalyst fosters the diffusion of N2 molecules and the aerophilic characteristic helps N2 adsorption, which can effectively suppress the HER. The active metal center is present in the primary sphere available for the NRR with a viable amount of H+ to achieve a substantially high faradaic efficiency (FE) of 49.3% at -0.3 V vs. RHE. DFT calculations were performed to find out the rate determining step and to explore the full energy pathway. A DFT study indicates that the NRR process follows an alternating pathway, which was further supported by an in situ FTIR study by isolating the intermediates. This work provides insights into designing a catalyst with hydrophobic moieties in the second coordination sphere together with the aerophilic nature of the catalyst that helps to improve the overall FE of the NRR by eliminating the HER.

Selective Electrocatalytic Oxidation of Nitrogen to Nitric Acid Using Manganese Phthalocyanine.

Ammonia is produced through the energy-intensive Haber-Bosch process, which undergoes catalytic oxidation for the production of commercial nitric acid by the senescent Ostwald process. The two energy-intensive industrial processes demand for process sustainability. Hence, single-step electrocatalysis offers a promising approach toward a more environmentally friendly solution. Herein, we report a 10-electron pathway associated one-step electrochemical dinitrogen oxidation reaction (N2OR) to nitric acid by manganese phthalocyanine (MnPc) hollow nano-structures under ambient conditions. The catalyst delivers a nitric acid yield of 513.2 µmol h-1 gcat-1 with 33.9% Faradaic efficiency @ 2.1 V versus reversible hydrogen electrode. The excellent N2OR performances are achieved due to the specific-selectivity, presence of greater number of exposed active sites, recyclability, and long period stability. The extended X-ray absorption fine structure confirms that Mn atoms are coordinated to the pyrrolic and pyridinic nitrogen via Mn-N4 coordination. Density functional theory-based theoretical calculations confirm that the Mn-N4 site of MnPc is the main active center for N2OR, which suppresses the oxygen evolution reaction. This work provides a new arena about the successful example of one step nitric acid production utilizing a Mn-N4 active site-based metal phthalocyanine electrocatalyst by dinitrogen oxidation for the development of a carbon-neutral sustainable society.

Oxygen Functionalization-Induced Charging Effect on Boron Active Sites for High-Yield Electrocatalytic NH3 Production.

Ammonia has been recognized as the future renewable energy fuel because of its wide-ranging applications in H2 storage and transportation sector. In order to avoid the environmentally hazardous Haber-Bosch process, recently, the third-generation ambient ammonia synthesis has drawn phenomenal attention and thus tremendous efforts are devoted to developing efficient electrocatalysts that would circumvent the bottlenecks of the electrochemical nitrogen reduction reaction (NRR) like competitive hydrogen evolution reaction, poor selectivity of N2 on catalyst surface. Herein, we report the synthesis of an oxygen-functionalized boron carbonitride matrix via a two-step pyrolysis technique. The conductive BNCO(1000) architecture, the compatibility of B-2pz orbital with the N-2pz orbital and the charging effect over B due to the C and O edge-atoms in a pentagon altogether facilitate N2 adsorption on the B edge-active sites. The optimum electrolyte acidity with 0.1 M HCl and the lowered anion crowding effect aid the protonation steps of NRR via an associative alternating pathway, which gives a sufficiently high yield of ammonia (211.5 µg h-1 mgcat-1) on the optimized BNCO(1000) catalyst with a Faradaic efficiency of 34.7% at - 0.1 V vs RHE. This work thus offers a cost-effective electrode material and provides a contemporary idea about reinforcing the charging effect over the secured active sites for NRR by selectively choosing the electrolyte anions and functionalizing the active edges of the BNCO(1000) catalyst.

Descriptors and graphical construction for in silico design of efficient and selective single atom catalysts for the eNRR.

The electrochemical nitrogen reduction reaction (eNRR) offers the possibility of ammonia synthesis under mild conditions; however, it suffers from low yields, a competing hydrogen evolution reaction pathway, and hydrogen poisoning. We present a systematic approach toward screening single atom catalysts (SACs) for the eNRR, by focusing on key parameters computed from density functional theory and relationships between them. We illustrate this by application to 66 model catalysts of the types, TM-Pc, TM-N X C Y , and TM-N3, where TM is a 3d transition metal or molybdenum. We identified the best SACs as Sc-Pc, Cr-N4, Mn-Pc, and Fe-N2C2; these show eNRR selectivity over the HER and no hydrogen poisoning. The catalysts are identified through multi-parameter optimization which includes the condition of hydrogen poisoning. We propose a new electronic descriptor Oval, the valence electron occupancy of the metal center that exhibits a volcano-type relationship with eNRR overpotential. Our multi-parameter optimization approach can be mapped onto a simple graphical construction to find the best catalyst for the eNRR over the HER and hydrogen poisoning.

Lewis acid-dominated aqueous electrolyte acting as co-catalyst and overcoming N2 activation issues on catalyst surface.

The growing demands for ammonia in agriculture and transportation fuel stimulate researchers to develop sustainable electrochemical methods to synthesize ammonia ambiently, to get past the energy-intensive Haber-Bosch process. However, the conventionally used aqueous electrolytes limit N2 solubility, leading to insufficient reactant molecules in the vicinity of the catalyst during electrochemical nitrogen reduction reaction (NRR). This hampers the yield and production rate of ammonia, irrespective of how efficient the catalyst is. Herein, we introduce an aqueous electrolyte (NaBF4), which not only acts as an N2-carrier in the medium but also works as a full-fledged "co-catalyst" along with our active material MnN4 to deliver a high yield of NH3 (328.59 µg h-1 mgcat-1) at 0.0 V versus reversible hydrogen electrode. BF3-induced charge polarization shifts the metal d-band center of the MnN4 unit close to the Fermi level, inviting N2 adsorption facilely. The Lewis acidity of the free BF3 molecules further propagates their importance in polarizing the N≡N bond of the adsorbed N2 and its first protonation. This push-pull kind of electronic interaction has been confirmed from the change in d-band center values of the MnN4 site as well as charge density distribution over our active model units, which turned out to be effective enough to lower the energy barrier of the potential determining steps of NRR. Consequently, a high production rate of NH3 (2.45 × 10-9 mol s-1 cm-2) was achieved, approaching the industrial scale where the source of NH3 was thoroughly studied and confirmed to be chiefly from the electrochemical reduction of the purged N2 gas.

Enhanced energy storage performance and theoretical studies of 3D cuboidal manganese diselenides embedded with multiwalled carbon nanotubes.

The burst of energy produced from the sustainable energy sources need to be harnessed by energy storage systems. Development of novel and advanced energy storage devices such as supercapacitors discover an enormous future ahead. Recently, hybrid supercapacitors (electric double layer capacitor (EDLC) and pseudocapacitors) trend to be used as energy storage interfaces for their improved efficacy in energy density without altering the power density. In the ongoing workplan, transition metal selenides MnSe2 and its hybrid with multiwalled carbon nanotubes (MWCNTs) are synthesized by a simplistic hydrothermal protocol. Certainly, cubic phases of MnSe2-MWCNT(MS/CNT) manifested superior electrochemical performance in both symmetric and asymmetric full cell configurations in contrast to prestine MnSe2(MS). The asymmetric MS/CNT cell achieved an excellent charge storage capability with an high energy density of 39.45 Wh kg-1 at a power density of 2.25 kW kg-1 maintaining an energy density of 14.5 Wh kg-1 at a high power density of 4.5 kWh kg-1 and also revealed long term stability over 5000 consecutive charge/discharge cycles (capacitance retention of 95.2%). Furthermore, the preferable growth along (200) direction in the presence of MWCNTs favoured in enriching the supercapacitive property of MS. The quantum capacitance of MnSe2surfaces and MS/CNT heterostructure has been estimated using density functional theory simulation to confirm the experimental outcomes. Theoretical investigation simultaneously exposed the contribution of (200) plane of MnSe2 and MWCNTs cultured in enhanced DOS (density of states) near the Fermi level that remarkably promoted the energy storage efficiency of MS/CNT.

Scalable Production of Cobalt Phthalocyanine Nanotubes: Efficient and Robust Hollow Electrocatalyst for Ammonia Synthesis at Room Temperature.

Electrocatalytic ammonia (NH3) synthesis through the nitrogen reduction reaction (NRR) under ambient conditions presents a promising alternative to the famous century-old Haber-Bosch process. Designing and developing a high-performance electrocatalyst is a compelling necessity for electrochemical NRR. Specific transition metal based nanostructured catalysts are potential candidates for this purpose owing to their attributes such as higher actives sites, specificity as well as selectivity and electron transfer, etc. However, due to the lack of a well-organized morphology, lower activity, selectivity, and stability of the electrocatalysts make them ineffective at producing a high NH3 yield rate and Faradaic efficiency (FE) for further development. In this work, stable ß-cobalt phthalocyanine (CoPc) nanotubes (NTs) have been synthesized by a scalable solvothermal method for electrochemical NRR. The chemically synthesized CoPc NTs show excellent electrochemical NRR due to high specific area, greater number of exposed active sites, and specific selectivity of the catalyst. As a result, CoPc NTs produced a higher NH3 yield of 107.9 µg h-1 mg-1cat and FE of 27.7% in 0.1 M HCl at -0.3 V vs RHE. The density functional theory calculations confirm that the Co center in CoPc is the main active site responsible for electrochemical NRR. This work demonstrates the development of hollow nanostructured electrocatalysts in large scale for N2 fixation to NH3.