Lin-Bo Huang

Sodium chloride-assisted green synthesis of a 3D Fe–N–C hybrid as a highly active electrocatalyst for the oxygen reduction reaction

To promote the oxygen reduction reaction (ORR) on a non-precious-metal catalyst, integrating two-dimensional (2D) nanosheets and one-dimensional (1D) nanotubes in one catalyst is considered as one of the desirable approaches since this hybrid architecture can host more useful active sites and enhance mass/electron transfer. Herein, we demonstrated a sodium chloride-assisted strategy for the in situ synthesis of a three-dimensional (3D) hybrid of carbon nanosheets and nanotubes. The micrometer-scale sodium chloride (NaCl) crystal acted as a recyclable skeleton to adsorb the precursors on its surfaces, which assisted the formation of micrometer-sized graphitic carbon nanosheets with nanometer thickness by the template effect during the pyrolysis, and iron-based nanocrystals with a size of tens of nanometers by helping the distribution of iron sources and preventing their aggregation. The small iron-based nanocrystals favored the growth of long CNTs connected to carbon nanosheets and the outmigration of carbon atoms during the cooling process, which led to the formation of carbon-layer encapsulated metallic iron nanoparticles between the carbon nanosheets or inside the carbon nanotubes. Benefiting from these features, the developed hybrid exhibited a significantly enhanced electrocatalytic activity and durability for the ORR. The results may open up opportunities for exploring cost-effective high-performance electrocatalysts for energy applications.

Encased Copper Boosts the Electrocatalytic Activity of N-Doped Carbon Nanotubes for Hydrogen Evolution

Nitrogen (N)-doped carbons combined with transition-metal nanoparticles are attractive as alternatives to the state-of-the-art precious metal catalysts for hydrogen evolution reaction (HER). Herein, we demonstrate a strategy for fabricating three-dimensional (3D) Cu-encased N-doped carbon nanotube arrays which are directly grown on Cu foam (Cu@NC NT/CF) as a new efficient HER electrocatalyst. Cu nanoparticles are encased here instead of common transition metals (Fe, Co, or Ni) for pursuing a well-controllable morphology and an excellent activity by taking advantage of its more stable nature at high temperature and in acidic or alkaline electrolyte. It is discovered that metallic Cu exhibits strong electronic modulation on N-doped carbon to boost its electrocatalytic activity for HER. Such a nanostructure not only offers plenty of accessible highly active sites but also provides a 3D conductive open network for fast electron/mass transfer and facilitates gas escape for prompt mass exchange. As a result, the Cu@NC NT/CF electrode exhibits superior HER performance and durability, outperforming most of the reported M@NC materials. Furthermore, the etching experiments together with X-ray photoelectron spectroscopy (XPS) analysis reveal that the electronic modulation from encased Cu significantly enhances the HER activity of N-doped carbon. These findings open up opportunities for exploring other Cu-based nanomaterials as efficient electrocatalysts and understanding their catalytic processes.

Tuning the branches and composition of PtCu nanodendrites through underpotential deposition of Cu towards advanced electrocatalytic activity

Controlled synthesis of Pt-based bimetallic nanocrystals with a tunable size and structure has demonstrated great potential to advance their electrocatalytic performances. We present herein a facile but effective strategy for the rapid aqueous synthesis of PtCu nanodendrites (NDs) with advanced electrocatalytic performance. The systematical investigation on the influence of reaction conditions on the formation of PtCu NDs reveals that the underpotential deposition of Cu not only accelerates the growth of NDs but also significantly modulates their size and branch structure as well as their composition. Electrochemical tests demonstrate that Pt55Cu45 NDs with a smaller size and fewer branches but a higher content of Cu exhibit the highest electrocatalytic activity for both the oxygen reduction reaction and the methanol oxidation reaction, compared with Pt92Cu8 NDs, Pt NDs and commercial Pt/C. These results may inspire the engineering of a wide range of metallic alloyed nanocrystals to advance their electrocatalytic performances for diverse applications.

Microbial-Phosphorus-Enabled Synthesis of Phosphide Nanocomposites for Efficient Electrocatalysts

Transition-metal phosphides have recently been identified as low-cost and efficient electrocatalysts that are highly active for the hydrogen evolution reaction. Unfortunately, to achieve a controlled phosphidation of nonprecious metals toward a desired nanostructure of metal phosphides, the synthetic processes usually turned complicated, high-cost, and even dangerous due to the reaction chemistry related to different phosphorus sources. It becomes even more challenging when considering the integration of those active metal phosphides with the structural engineering of their conductive matrix toward a favorable architecture for optimized catalytic performance. Herein, we identified that the biomass itself could act as an effective synthetic platform for the construction of supported metal phosphides by recovering its inner phosphorus upon reacting with transition-metals ions, forming well-dispersed, highly active nanoparticles of metal phosphides incorporated in the nanoporous carbon matrix, which promised high catalytic activity in the hydrogen evolution reaction. Our synthetic protocol not only provides a simple and effective strategy for the construction of a large variety of highly active nanoparticles of metal phosphides but also envisions new perspectives on an integrated utilization of the essential ingredients, particularly phosphorus, together with the innate architecture of the existing biomass for the creation of functional nanomaterials toward sustainable energy development.

In situ transformation of Cu2O@MnO2 to Cu@Mn(OH)2 nanosheet-on-nanowire arrays for efficient hydrogen evolution

The development of new non-precious metal catalysts and understanding the origin of their activity for the hydrogen evolution reaction (HER) are essential for rationally designing highly active low-cost catalysts as alternatives to state-of-the-art precious metal catalysts. Herein, manganese oxide/hydroxide was demonstrated as a highly active electrocatalysts for the HER by fabricating MnO2 nanosheets coated with Cu2O nanowire arrays (Cu2O@MnO2 NW@NS) on Cu foam followed by an in situ chronopotentiometry (CP) treatment. It was discovered that the in situ transformation of Cu2O@MnO2 into Cu@Mn(OH)2 NW@NS by the CP treatment drastically boosted the catalytic activity for the HER due to an enhancement of its intrinsic activity. Together with the benefits from such three-dimensional (3D) core–shell arrays for exposing more accessible active sites and efficient mass and electron transfers, the resulting Cu@Mn(OH)2 NW@NS exhibited excellent HER activity and outstanding durability in terms of a low overpotential of 132 mV vs. RHE at 10 mA/cm2. Overall, we expect these findings to generate new opportunities for the exploration of other Mn-based nanomaterials as efficient electrocatalysts and enable further understanding of their catalytic processes.

Self-supported 3D Nanoporous Ni/V2O3 Hybrid Nanoplate Assemblies for Highly Efficient Electrochemical Hydrogen Evolution

Nickel-based non-noble-metal materials have emerged as promising catalysts for electrochemical hydrogen production in view of their attractive intrinsic activities, electrical properties and low cost. Exploring new candidates for further improving the performances of nickel-based catalysts and understanding the structure–activity relationship are still necessary to reduce the overpotential of the hydrogen evolution reaction (HER) thus advancing their application in electrochemical water splitting. Herein, we developed a facile two-step self-templated strategy for fabricating a three-dimensional (3D) nanoporous nickel/vanadium oxide (Ni/V2O3) nanoplate assembly as a new efficient catalyst for alkaline HER. It is found that by controllably annealing the Ni–V–O assembly as a single precursor, Ni and V2O3 components are uniformly integrated in the nanoporous composite, showing a synergistically enhancing effect on the HER. The resulting 3D nanoporous structure not only creates numerous active sites accessible for the HER but also provides a conductive open network towards efficient electron/mass transport. Consequently, the nanoporous Ni/V2O3 nanoplate assembly exhibits excellent catalytic performance for alkaline HER in terms of a low overpotential of 61 mV at 10 mA cm−2 and a small Tafel slope of 79.7 mV dec−1 together with excellent long-term durability. These findings provide new insights into good design and construction of other highly active catalysts for diverse applications.