Search

MoSe2 as one graphene-like 2D transition metal selenide has attracted great attention. However, its application for the hydrogen evolution reaction (HER) is still restricted by the poor electrical conductivity and structural restacking. In this work, an excellent electrocatalyst for hydrogen production is developed based on the in situ synthesis of V-doped MoSe2 confined on carbon black nanoparticles (denoted as V-MoSe2/CB) via a sol–gel process. The characterization results show that the carbon black nanoparticles can protect the V-MoSe2 nanosheets from agglomeration, resulting in ultra-thin thickness and short vertical lattice arrays. Meanwhile, density functional theory (DFT) calculations indicate that vanadium doping can optimize the electronic structure of MoSe2. Accordingly, compared to the pure MoSe2, V-MoSe2 and MoSe2/CB electrocatalysts, V-MoSe2/CB exhibits improved electrocatalytic activity with a small overpotential of 166 mV at −10 mA cm−2 and a small Tafel slope of 65 mV dec−1. This work paves a new way for improving the HER performance through synergistic morphology, structure and electronic regulation. [ABSTRACT FROM AUTHOR]

The construction of highly active and stable transition phosphide-based materials is widely regarded as an alternative approach to the use of Pt-based catalysts in the field of electrocatalytic hydrogen evolution. Herein, self-supported heterostructure Co–Ni phosphides (denoted as CoxNi1−x-P) were synthesized with different metal ratios by a low temperature electrodeposition strategy. Impressively, the optimized heterogeneous Co0.5Ni0.5-P nanocomposites displayed outstanding hydrogen evolution performance, with low overpotentials of 67 mV and 181 mV to deliver current densities of 10 mA cm−2 and 100 mA cm−2 in alkaline electrolyte. X-ray photoelectron spectroscopy revealed the optimized electronic structure of Co0.5Ni0.5-P, which led to an improvement in the conductivity. Density functional theory calculations demonstrated that the Co0.5Ni0.5-P heterostructure could provide a more optimal water-dissociation-related Volmer process for hydrogen evolution reaction (HER), in which water molecules could be easily activated on Co0.5Ni0.5-P with a low energy barrier. Moreover, the downshift of the d-band center confirmed the optimized H adsorption, further accelerating the HER kinetics. [ABSTRACT FROM AUTHOR]

Covalent triazine frameworks (CTFs) involving donor-π bridge-acceptor (D–π–A) motifs with the electron-withdrawing triazine unit as the acceptor have been regarded as one of the most promising materials for photocatalytic water splitting. The intrinsic features of π-bridges play a critical role in tailoring the polymer properties as well as the photocatalytic performance. Introducing suitable conjugated units as the π-bridge is expected to effectively tune the electronic structure of the resultant D–π–A CTFs and facilitate photo-generated charge separation. However, systematic studies on how different π-bridges would influence the photoelectronic properties of D–π–A type CTFs are still limited. Herein, three types of CTFs with well-defined D–π–A structures named Ben-CTF, BenT-CTF and BenP-CTF were synthesized to investigate the effects of different π-bridges (benzene, thiophene and pyridine units) on the performance of photocatalytic water splitting for hydrogen production. Comprehensive experiments and density functional theory (DFT) calculations revealed that BenP-CTF with the pyridine unit as the π-bridge exhibited superior charge migration ability and higher photocatalytic hydrogen evolution reaction (HER) rates compared to the other CTFs. This work may provide a reference for the rational design and controllable synthesis of CTF materials for efficient photocatalysis. [ABSTRACT FROM AUTHOR]

For effective overall water splitting (OWS) in alkaline media, a novel Ru-doped bimetal oxide (Ru-NiCo2O4) catalyst deposited onto a conductive nickel foam (NF) is fabricated by a multi-step hydrothermal reaction, ion exchange, and subsequent annealing process. The distinctive 3D nanoneedle-like arrays not only provide an even distribution of Ru decorated NiCo2O4, but also expose additional active sites, facilitating electron transport and improving reaction kinetics. Besides, density functional theory (DFT) studies elucidate the electronic structure regulation in Ru-NiCo2O4 and the modification of the d-band center optimizes H* adsorption energy, which considerably increased the hydrogen production efficiency. Considering the aforementioned advantages, the as-prepared Ru-NiCo2O4 electrocatalyst exhibits greatly improved catalytic activity, requiring only 25 mV and 249 mV at 10 mA cm−2 for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, as well as robust stability. Amazingly, the Ru-NiCo2O4 electrode in a two-electrode alkaline electrolyzer only needs 1.55 V to produce 10 mA cm−2, making it more efficient than the commercial RuO2‖‖Pt/C electrode (1.62 V). More importantly, 0.33 M urea only needs a low voltage of 1.427 V to drive the urine-mediated electrolysis, which is about 123 mV less than the urea-free electrolysis cell. This work presents an effective electronic structure engineering approach based on heteroatom doping that may be extended to design and fabricate novel high-performance OWS catalysts. [ABSTRACT FROM AUTHOR]

Rationally designing ternary transition-metal phosphides (TMPs) for the hydrogen evolution reaction (HER) is desirable but remains a significant challenge. Herein, ternary FeCoNiP encapsulated in a porous carbon shell, coupled with N-doped carbon nanotubes (FeCoNiP@NCNTs) are synthesized via a simple pyrolysis–phosphatization strategy derived from FeCoNi-MOF-100@dicyandiamide. Because Co/Ni enters the FeP lattice, FeCoNiP@NCNTs show a favorable catalytic performance towards the HER with low overpotential values of 86.7 and 233.5 mV at 10 mA cm−2 in acidic and alkaline media, respectively, surpassing the HER performance of FeP@NCNTs, FeCoP@NCNTs, and FeNiP@NCNTs. Impressively, FeCoNiP@NCNTs display adequate acid-resistance capacity during the HER process, with nearly negligible decay due to the thin graphitized carbon shell structure with a thickness of 11.5–20.3 nm. The results of experiments, structural characterization, and density functional theory (DFT) calculations demonstrate that Co/Ni co-doping can modulate the adsorption and dissociation processes of H+ and downshift the d-band center of FeP. This work proposes a strategy for fabricating ternary TMP catalysts with heterogeneous structures for the HER. [ABSTRACT FROM AUTHOR]

For energy conversion and storage, the electrochemical oxygen evolution process (OER) is the crucial half-reaction process. The amphiprotic characteristics of sulfamic acid are due to its amine and sulphonic acid functional groups. Metal-based catalysts can be utilized to fabricate bimetallic and dual-ligand linked FeCo–SA/DABCO nanosheets with improved catalytic performance. The crystal structure of bimetallic FeCo–SA/DABCO consisted of alternating organic hydrocarbons SA and DABCO and inorganic metal–oxygen layers. FeCo–SA/DABCO provided an overpotential (η10) of 290 mV to achieve a current density of 10 mA cm−2 together with a small Tafel slope of 112.79 mV dec−1 and also exhibited long-term durability. Electrochemical results showed that FeCo–SA/DABCO was superior to FeCo–SA and Co–SA/DABCO. Density functional theory calculations indicated that the theoretical overpotential of FeCo–SA/DABCO is 0.62 eV, which was lower than that of FeCo–SA. The introduction of composite SA/DABCO ligands can change the rate-determining step, which can improve the conductivity and reduce the reaction barrier for the formation of intermediates, thereby affecting the catalytic activity and changing the overall electron transfer capacity. [ABSTRACT FROM AUTHOR]

Generation of molecular hydrogen by electrochemical water splitting is a promising approach, and its efficiency strictly depends on the electrocatalyst used. Therefore, it is an ongoing challenge to design materials having improved the electrocatalytic behaviour towards hydrogen evolution reaction. Here, using Co-MOF [Co4(BTC)3(BIm)6] as starting precursor, graphitic carbon encapsulated CoSe2 nanorods have been prepared through a single step selenization method. The carbon network in the CoSe2/C hybrid nanostructure forms channels, facilitating the accessibility of the electrolyte ions and maximizing the utilization of catalytic active centers. This makes the hybrid to show higher electrochemical accessible surface area, lower charge transfer resistance, and improved catalytic durability towards the electrocatalytic hydrogen evolution reaction with respect to the non-noble metal (graphite rod) counter electrode. Specifically, it needs only 253 mV of overpotential to reach the benchmarked current density (10 mA cm−2) with a lower Tafel slope. Further, the experimental findings have been supported by the theoretical analysis of the structure and electronic properties of CoSe2 and CoSe2/C hybrid by density functional theory (DFT) simulations. The interaction between CoSe2 and C is due to charge transfer from Co 3d orbital and Se 4p orbital of CoSe2 to the 2p orbital of carbon. Also, populated electronic states near Fermi level for C doped CoSe2 may infer towards increased conductivity of the material. Computed overpotentials for HER activities show a qualitative order of CoSe2/C < CoSe2, matching nicely with the experimental data. The synergic effect of increased conductivity, improved surface area, and superior electrocatalytic activity due to C doping is responsible for the superior HER catalytic performance. [ABSTRACT FROM AUTHOR]