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Hematite (α-Fe 2 O 3 ) is a promising transition metal oxide for various energy conversion and storage applications due to its advantages of low cost, high abundance, and good chemical stability. However, its low carrier mobility and electrical conductivity have hindered the wide application of hematite-based devices. Fundamentally, this is mainly caused by the formation of small polarons, which show conduction through thermally activated hopping. Atomic doping is one of the most promising approaches for improving the electrical conductivity in hematite. However, its impact on the carrier mobility and electrical conductivity of hematite at the atomic level remains to be illusive. In this work, through a kinetic Monte-Carlo sampling approach for diffusion coefficients combined with carrier concentrations computed under charge neutrality conditions, we obtained the electrical conductivity of the doped hematite. We considered the contributions from individual Fe–O layers, given that the in-plane carrier transport dominates. We then studied how different dopants impact the carrier mobility in hematite using Sn, Ti, and Nb as prototypical examples. We found that the carrier mobility change is closely correlated with the local distortion of Fe–Fe pairs, i.e. the more stretched the Fe–Fe pairs are compared to the pristine systems, the lower the carrier mobility will be. Therefore, elements which limit the distortion of Fe–Fe pair distances from pristine are more desired for higher carrier mobility in hematite. The calculated local structure and pair distribution functions of the doped systems have remarkable agreement with the experimental EXAFS measurements on hematite nanowires, which further validates our first-principles predictions. Our work revealed how dopants impact the carrier mobility and electrical conductivity of hematite and provided practical guidelines to experimentalists on the choice of dopants for the optimal electrical conductivity of hematite and the performance of hematite-based devices. 

Sustainable hydrogen gas production is critical for future fuel infrastructure. Here, a series of phosphorous-doped carbon nitride materials were synthesized by thermal annealing of urea and ammonium hexafluorophosphate, and platinum was atomically dispersed within the structural scaffold by thermal refluxing with Zeise's salt forming Pt–N/P/Cl coordination interactions, as manifested in X-ray photoelectron and absorption spectroscopic measurements. The resulting materials were found to exhibit markedly enhanced electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media, as compared to the P-free counterpart. This was accounted for by P doping that led to a significantly improved charge carrier density within C 3 N 4 , and the sample with the optimal P content showed an overpotential of only −22 mV to reach the current density of 10 mA cm −2 , lower than that of commercial Pt/C (−26 mV), and a mass activity (7.1 mA μg−1Pt at −70 mV vs. reversible hydrogen electrode) nearly triple that of the latter. Results from the present study highlight the significance of P doping in the manipulation of the electronic structures of metal/carbon nitride nanocomposites for high-performance HER electrocatalysis. 

Carbon nanocomposites based on transition-metal oxides have been attracting extensive attention as cost-effective catalysts towards the oxygen reduction reaction (ORR). However, the activity remains subpar as compared to state-of-the-art platinum catalysts. One way to enhance the ORR performance is to dope a second metal into the nanocomposite to manipulate the electronic structure and hence the interactions with key reaction intermediates. Herein, dual metal (Ru and Fe) and nitrogen codoped carbon (RuFe-NC) nanocomposites were synthesized by controlled pyrolysis of a Fe–Ru–Fe trinuclear complex along with zeolitic imidazolate framework-8. The obtained porous nanocomposites consisted of Ru-doped Fe 2 O 3 nanoparticles embedded within a carbon scaffold, and exhibited an ORR activity in alkaline media rivaling that of commercial Pt/C, which was also markedly better than those of the monometallic counterparts and nanocomposites prepared with a simple mixture of the individual monometallic compound precursors. Structural characterization suggests that the use of the trinuclear complex facilitated the atomic dispersion of ruthenium within the iron oxide nanoparticles and charge transfer between the metal centers led to a high ORR activity. Results from this study suggest that rational design of heteronuclear complexes may be a unique strategy in the structural engineering of carbon-metal nanocomposites for high-performance electrocatalysis. 

Iron single atom catalysts have emerged as one of the most active electrocatalysts towards the oxygen reduction reaction (ORR), but the unsatisfactory durability and limited activity for the oxygen evolution reaction (OER) has hampered their commercial applications in rechargeable metal–air batteries. By contrast, cobalt-based catalysts are known to afford excellent ORR stability and OER activity, due to the weak Fenton reaction and low OER Gibbs free energy. Herein, a bimetal hydrogel template is used to prepare carbon aerogels containing Fe–Co bimetal sites (NCAG/Fe–Co) as bifunctional electrocatalysts towards both ORR and OER, with enhanced activity and stability, as compared to the monometal counterparts. High-resolution transmission electron microscopy, elemental mapping and X-ray photoelectron spectroscopy measurements demonstrate homogeneous distributions of the metal centers within defected carbon lattices by coordination to nitrogen dopants. X-ray absorption spectroscopic measurements, in combination with other results, suggest the formation of FeN 3 and CoN 3 moieties on mutually orthogonal planes with a direct Fe–Co bonding interaction. Electrochemical measurements show that NCAG/Fe–Co delivers a small ORR/OER potential gap of only 0.64 V at the current density of 10 mA cm −2 , 60 mV lower than that (0.70 V) with commercial Pt/C and RuO 2 catalysts. When applied in a flexible Zn–air battery, the dual-metal NCAG/Fe–Co catalyst also shows a remarkable performance, with a high open-circuit voltage of 1.47 V, a maximum power density of 117 mW cm −2 , as well as good rechargeability and flexibility. Results from this study may offer an ingenious protocol in the design and engineering of highly efficient and durable bifunctional electrocatalysts based on dual metal-doped carbons.