Yingjun Sun

Graphene/Intermetallic PtPb Nanoplates Composites for Boosting Electrochemical Detection of H2O2 Released from Cells

Rational design and construction of electrocatalytic nanomaterials is vital for improving the sensitivity and selectivity of nonenzymatic electrochemical sensors. Here, we report a novel graphene supported intermetallic PtPb nanoplates (PtPb/G) nanocomposite as an enhanced electrochemical sensing platform for high-sensitivity detection of H2O2 in neutral solution and also released from the cells. The intermetallic PtPb nanoplates are first synthesized via a simple wet-chemistry process and subsequently assembled on graphene via a solution-phase self-assembly approach. The obtained nanocomposite exhibits excellent electrocatalytic activity for the electrochemical reduction of H2O2 in a half-cell test and can detect H2O2 with a wide linear detection range of 2 nM to 2.5 mM and a very low detection limit of 2 nM. Under the same conditions, the sensitivity of PtPb/G for the detection of H2O2 is more than 12.7 times higher than that of commercial Pt/C. The high-density of electrocatalytic active sites on the unique PtPb nanoplates and the synergistic effect between PtPb nanoplates and graphene appear to be the main factors in contributing to the outstanding electroanalytical performance. The PtPb/G can be also used for the practical detection of H2O2 released from Raw 264.7 cells.

The marriage and integration of nanostructures with different dimensions for synergistic electrocatalysis

The search for new ways to make inexpensive and efficient electrocatalysts to replace precious-metal platinum catalysts for oxygen reduction and water splitting is still a great challenge. Here, we report a facile and effective strategy for the rational design and construction of three-dimensional (3D) architectures for superior electrocatalysis through the integration of one-dimensional (1D) electrospun carbon nanofibers (CNFs), 1D carbon nanotubes (CNTs) and 0D oxygen-deficient Mn3Co7–Co2Mn3O8 nanoparticles (NPs). The rationale behind the marriage and integration of nanostructures with different dimensions presented in this work is that during heat treatment, the in situ-produced CoMnO NPs are partly reduced to Co2Mn3O8 by a carbon precursor with an amount of metallic Mn3Co7 formed at the interface between the Co2Mn3O8 NPs and carbon, which can act as the catalysts for the growth of 3D CNT forests. The 3D CoMnO@CNT/CNF architectures exhibit superior electrocatalytic activity and stability for the oxygen reduction, oxygen evolution and hydrogen evolution reactions. The remarkable electrochemical properties are mainly attributed to the synergistic effects from the engineering of oxygen-deficient binary CoMn oxide NPs with exposed active sites and 3D hierarchical porous structures consisting of branched CNTs and interconnected CNFs. The present work demonstrates the first example of integrating multiple active catalytic centers onto/into 3D architectures for developing highly efficient non-precious metal nanocatalysts for electrochemical energy devices.

Stable High‐Index Faceted Pt Skin on Zigzag‐Like PtFe Nanowires Enhances Oxygen Reduction Catalysis

Selectively exposing active surfaces and judiciously tuning the near-surface composition of electrode materials represent two prominent means of promoting electrocatalytic performance. Here, a new class of Pt3 Fe zigzag-like nanowires (Pt-skin Pt3 Fe z-NWs) with stable high-index facets (HIFs) and nanosegregated Pt-skin structure is reported, which are capable of substantially boosting electrocatalysis in fuel cells. These unique structural features endow the Pt-skin Pt3 Fe z-NWs with a mass activity of 2.11 A mg-1 and a specifc activity of 4.34 mA cm-2 for the oxygen reduction reaction (ORR) at 0.9 V versus reversible hydrogen electrode, which are the highest in all reported PtFe-based ORR catalysts. Density function theory calculations reveal a combination of exposed HIFs and formation of Pt-skin structure, leading to an optimal oxygen adsorption energy due to the ligand and strain effects, which is responsible for the much enhanced ORR activities. In contrast to previously reported HIFs-based catalysts, the Pt-skin Pt3 Fe z-NWs maintain ultrahigh durability with little activity decay and negligible structure transformation after 50 000 potential cycles. Overcoming a key technical barrier in electrocatalysis, this work successfully extends the nanosegregated Pt-skin structure to nanocatalysts with HIFs, heralding the exciting prospects of high-effcient Pt-based catalysts in fuel cells.

Defects and Interfaces on PtPb Nanoplates Boost Fuel Cell Electrocatalysis

Nanostructured Pt is the most efficient single-metal catalyst for fuel cell technology. Great efforts have been devoted to optimizing the Pt-based alloy nanocrystals with desired structure, composition, and shape for boosting the electrocatalytic activity. However, these well-known controls still show the limited ability in maximizing the Pt utilization efficiency for achieving more efficient fuel cell catalysis. Herein, a new strategy for maximizing the fuel cell catalysis by controlling/tuning the defects and interfaces of PtPb nanoplates using ion irradiation technique is reported. The defects and interfaces on PtPb nanoplates, controlled by the fluence of incident C+ ions, make them exhibit the volcano-like electrocatalytic activity for methanol oxidation reaction (MOR), ethanol oxidation reaction (EOR), and oxygen reduction reaction (ORR) as a function of ion irradiation fluence. The optimized PtPb nanoplates with the mixed structure of dislocations, subgrain boundaries, and small amorphous domains are the most active for MOR, EOR, and ORR. They can also maintain high catalytic stability in acid solution. This work highlights the impact and significance of inducing/controlling the defects and interfaces on Pt-based nanocrystals toward maximizing the catalytic performance by advanced ion irradiation strategy.

Atomic-thick PtNi Nanowires Assembled on Graphene for High-Sensitivity Extra-Cellular Hydrogen Peroxide Sensors

H2O2 sensors with high sensitivity and selectivity are essential for monitoring the normal activities of cells. Inorganic catalytic nanomaterials show the obvious advantage in boosting the sensitivity of H2O2 sensors; however, the H2O2 detection limit of reported inorganic catalysts is still limited, which is not suitable for high-sensitivity detection of H2O2 in real cells. Herein, novel atomic-thick PtNi nanowires (NWs) were synthesized and assembled on reduced graphene oxide (rGO) via an ultrasonic self-assembly method to attain PtNi NWs/rGO composite for boosting the electroanalysis of H2O2. In 0.05 M phosphate-buffered saline (pH 7.4) solution, the as-prepared PtNi NWs/rGO shows an extraordinary performance in quantifying H2O2 in a wide range of concentrations from 1 nM to 5.3 mM. Significantly, the detection limit of PtNi NWs/rGO reaches unprecedented 0.3 nM at an applied potential of -0.6 V (vs Ag/AgCl), which enables the detection of traced amounts of H2O2 released from Raw 264.7 cells. The excellent performance of H2O2 detection on PtNi NWs/rGO is ascribed to the high-density active sites of atomic-thick PtNi NWs.

Ultrathin PtPd-Based Nanorings with Abundant Step Atoms Enhance Oxygen Catalysis

The lack of highly active and stable catalysts with low Pt usage for the oxygen reduction reaction (ORR) is a major barrier in realizing fuel cell-driven transportation applications. A general colloidal chemistry method is demonstrated for making a series of ultrathin PtPdM (M = Co, Ni, Fe) nanorings (NRs) for greatly boosting ORR catalysis. Different from the traditional ultrathin nanosheets, the ultrathin PtPdM NRs herein have a high portion of step atoms on the edge, high Pt utilization efficiency, and strong ligand effect from M to Pt and fast mass transport of reactants to the NRs. These key features make them exhibit greatly enhanced electrocatalytic activity for the ORR and the oxygen evolution reaction (OER). Among all the PtPdM NRs, the PtPdCo shows the highest ORR mass and specific activities of 3.58 A mg-1 and 4.90 mA cm-2 at 0.9 V versus reversible hydrogen electrode (RHE), 23.9 and 24.5-fold larger than those of commercial Pt/C in alkaline electrolyte, respectively. The theoretical calculations reveal that the oxygen adsorption energy (E O ) can be optimized under the presence of step atoms exposed on the edge and ligand effect induced by Co. They are stable under ORR conditions with negligible changes after 30 000 cycles.