Electrochemical Nitrogen Reduction to Ammonia at Ambient Condition on the (111) Facets of Transition Metal Carbonitrides.

We conducted Density Functional Theory calculations to investigate a class of materials with the goal of enabling nitrogen activation and electrochemical ammonia production under ambient conditions. The source of protons at the anode could originate from either water splitting or H2, but our specific focus was on the cathode reaction, where nitrogen is reduced into ammonia. We examined the conventional associative mechanism, dissociative mechanism, and Mars-van Krevelen mechanism on the (111) facets of the NaCl-type structure found in early transition metal carbonitrides, including Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Sc, Y, and W. We explored the catalytic activity by calculating the free energy of all intermediates along the reaction pathway and constructing free energy diagrams to identify the steps that determine the reaction's feasibility. Additionally, we closely examined the potential for catalyst poisoning within the electrochemical environment, considering the bias required to drive the reaction. Furthermore, we assessed the likelihood of catalyst decomposition and the potential for catalyst regeneration among the most intriguing carbonitrides. Our findings revealed that the only carbonitride catalyst considered here exhibiting both activity and stability, capable of self-regeneration and nitrogen-to-ammonia activation, is NbCN with a low potential-determining step energy of 0.58 eV. This material can facilitate ammonia formation via a mixed associative-MvK mechanism. In contrast, other carbonitrides of this crystallographic orientation are likely to undergo decomposition, reverting to their parent metals under operational conditions.

Nitrogen Reduction Reaction to Ammonia on Transition Metal Carbide Catalysts.

The development of a low-cost, energy-efficient, and environmentally friendly alternative to the currently utilized Haber-Bosch process to produce ammonia is of great importance. Ammonia is an essential chemical used in fertilizers and a promising high-density fuel source. The nitrogen reduction reaction (NRR) has been explored intensively as a potential avenue for ammonia production using water as proton source, but to this day a catalyst capable of producing this chemical at high Faradaic efficiency (FE) and commercial yield and rates has not been reported. Here, we investigate the activity of transition metal carbide (TMC) surfaces in the (100) facets of the rocksalt (RS) structure as potential catalysts for the NRR. In this study, we use density functional theory (DFT) to model reaction pathways, estimate stability, assess kinetic barriers, and compare adsorbate energies to determine the overall performance of each TMC surface. For pristine TMC surfaces (with no defects) we find that none of the studied TMCs possess both exergonic adsorption of nitrogen and the capability to selectively protonate nitrogen to form ammonia in the desired aqueous solution. ZrC, however, is shown to be a potential catalyst if used in a non-aqueous electrolyte. To circumvent the endergonic adsorption of nitrogen onto the surface, a carbon vacancy was introduced. This provides a well-defined high coordination active site on the surface. In the presence of a vacancy VC, NbC, and WC showed efficient nitrogen adsorption, selectivity towards ammonia, and a low overpotential (OP). NbC did, however, display an unfeasible kinetic barrier to nitrogen dissociation for ambient-condition purposes, and thus it is suggested for high tempearture/pressure ammonia synthesis. Both WC and VC in their RS (100) structure are promising materials for experimental investigations in aqueous electrolytes, and ZrC could potentially be interesting for non-aqueous electrolytic systems.

Optimizing Band Gap of Inorganic Halide Perovskites by Donor-Acceptor Pair Codoping.

Inorganic halide perovskites (IHPs) are promising candidates for applications in solar cell devices. However, the band gaps of most IHPs are too large, so that the energy conversion efficiency is limited. In this work, we proposed a donor-acceptor pair codoping scheme to reduce the band gaps Sn- and Pb-based IHPs, based on first-principles calculations. Interestingly, the donor-acceptor pair codoping in CsSnBr3 and CsPbI3 can produce band gaps of 1.2 and 1.1 eV, respectively, both of which are close to the optimal band gap for solar cell materials. The absorption coefficient of donor-acceptor pair codoped CsSnBr3 and CsPbI3 in the visible light region are large, which indicates that they are good light absorbers for applications in solar cell devices.

Design and characterization of a biomass template/SnO2 nanocomposite for enhanced adsorption of 2,4-dichlorophenol.

2,4-Dichlorophenol (2,4-DCP) is a hazardous chlorinated organic chemical derived from phenol that exerts serious effects on living organisms. In the present study, SnO2 templated with grapefruit peel carbon as a nanocomposite (SnO2@GPC) was designed via ball-milling, and its mechanism of 2,4-DCP adsorption in aqueous solution was determined. Batch adsorption experiments revealed that the maximum adsorption efficiency of SnO2@GPC occurred at 6.0 pH, 3 mg L-1 initial adsorbate concentration, 2 h contact time, and 293 K temperature. The SnO2@GPC nanocomposite and its non-tin-bearing counterpart, grapefruit derived char (@GPC), showed maximum adsorption capacities (QL) of 45.95 and 22.09 mg g-1 and partition coefficients of 41.77 and 10.83 mg g-1 µM-1, respectively. The adsorption of 2,4-DCP was best described by the Redlich-Peterson model followed by the Langmuir model with high correlation coefficients (R2 ≥ 0.96), and the adsorption kinetic data best fitted the pseudo-second-order model (R2 ≥ 0.98). The thermodynamic parameters indicated that the reaction was spontaneous, exothermic, and involved high affinity between SnO2@GPC and 2,4-DCP. The high desorption efficiency obtained (>80%) demonstrated the recyclability of the adsorbent. The enhanced QL of SnO2@GPC was due to the effective combination of GPC and SnO2. A thin porous layer of GPC on SnO2 nanoparticles provided effective channels, a large surface area, and an abundance of active sites for 2,4-DCP adsorption. Thus, the SnO2@GPC nanocomposite could potentially be used as a low-cost adsorbent to remove 2,4-DCP from water.