Conductive One-Dimensional Coordination Polymers with Tunable Selectivity for the Oxygen Reduction Reaction

Abstract

Conductive materials involving nonprecious metal coordination complexes as electrocatalysts for the oxygen reduction reaction (ORR) have received increasing attention in recent years. Herein, we reported efficient ORR electrocatalysts containing M-S 2 N 2 sites with tunable selectivity based on simple one-dimensional (1D) coordination polymers (CPs). The 1D CPs were synthesized from M(OAc) 2 and 2,5-diamino-1,4benzenedithiol (DABDT) by a solvent thermal method. Due to their good electrical conductivities (10 −6 −10 −2 S cm −1 ), the 1D CPs could be used as ORR catalysts in low catalytic amounts without the addition of carbon materials. Cobalt-based CPs showed a well-organized structure of nanosheets with Co-S 2 N 2 sites exposed and exhibited remarkable electrocatalytic ORR activity (E onset = 0.93 V vs reversible hydrogen electrode (RHE), E 1/2 = 0.82 V, n = 3.85, J L = 5.22 mA cm −2 , Tafel slope of 63 mV dec −1 ) in alkaline media. However, nickel-based CPs favored a 2e − ORR process with ∼87% H 2 O 2 selectivity and an E onset of 0.78 V. This work provides new opportunities for the construction of ORR catalysts based on conductive nonprecious metal CPs.

Atomic-Level Modulation-Induced Electron Redistribution in Co Coordination Polymers Elucidates the Oxygen Reduction Mechanism

“…In order to verify the regulation of suitable ligands in the charge of metal centers in MCPs, we synthesized Co-BTA, Co-DABDT, and Co-BTT via a facile complexation reaction under ambient conditions according to the previous report. − With the preparation of Co-DABDT as an example, the structure change before and after reaction can be illustrated by the Fourier transform infrared (FT-IR) spectrum. The disappearance of two representative peaks (HCl: 2500∼2800 cm –1 and S–H stretching vibration: 2500 cm –1 ) in DABDT·2HCl and the appearance of the N–H stretching vibration (−NH, 3300 cm –1 ) indicate that the −NH 2 and −SH of the DABDT ligand have coordinated with Co ions (Figure a). ,− In addition, the peaks around 1400–1500 cm –1 (benzene ring skeleton), 1250 cm –1 (C–N bond), and 1030 cm –1 (C–S bond) confirm the benzene ring structure, nitrogen-containing and sulfur-containing functional groups of Co-DABDT after coordination .…”

The crystal structure and oxygen reduction reaction of Ni(ii)-complex templated borate-sulfate and borate

“…At present, the exploration of ORR catalysts is mainly in non-precious metal based catalysts, such as single-atom catalysts, and metalorganic frameworks. [21][22][23][24][25][26][27][28][29][30][31] Cheng et al reported efficient ORR electrocatalysts containing M-S 2 N 2 sites with tunable selectivity based on simple one-dimensional coordination polymers. 25 Hu et al reported a sulfur-doped Fe/N/C catalyst, which was obtained by a template-sacrificing method.…”

“…[21][22][23][24][25][26][27][28][29][30][31] Cheng et al reported efficient ORR electrocatalysts containing M-S 2 N 2 sites with tunable selectivity based on simple one-dimensional coordination polymers. 25 Hu et al reported a sulfur-doped Fe/N/C catalyst, which was obtained by a template-sacrificing method. 26 Yang et al reported a Co-N/CNFs catalyst with high durability and desirable ORR activity.…”

Ionic Covalent Organosilicon Polymer Nanosheet for Selective and Sensitive Detection of Dopamine

“…This value indicates a bandgap energy between 0.5−2.5 eV, suggesting the HHTP-Si ICOP is a semiconductor. 33 The conductivity of the HHTP-Si ICOP under different temperatures was measured by linear sweep voltammetry with a pressed tablet by two-point probe method. As shown in Figure 4b, the conductivity value of HHTP-Si ICOP was calculated to be 3.94 × 10 −3 mS cm −1 at 30 °C, and it exhibited an Arrhenius-type increase with the raise of temperature.…”

“…The optical band gap of 1.76 eV was determined from the result of the Tauc plot (Figure a) that was calculated from the diffusion reflectance spectrum. This value indicates a bandgap energy between 0.5–2.5 eV, suggesting the HHTP-Si ICOP is a semiconductor . The conductivity of the HHTP-Si ICOP under different temperatures was measured by linear sweep voltammetry with a pressed tablet by two-point probe method.…”