Fabrication of 1D long chain-like metal porphyrin-based coordination complexes for high-efficiency hydrogen evolution and photoelectric response

https://doi.org/10.1016/j.ijhydene.2019.05.059Get rights and content

Highlights

  • 1D long chain-like porphyrin-based coordination complexes were fabricated.

  • 1D nanostructure is in favor of photogenerated charges separation and transfer.

  • The complexes have high-efficiency hydrogen evolution.

  • The complexes have better photoelectric response.

  • The complexes have great potential for electrocatalyst and photoelectric material.

Abstract

Hydrogen production from electrocatalytic water splitting has aroused extensive attention in many fields recently. Fabrication of low-cost and high-efficiency electrocatalysts are still an urgent and challenging work. Porphyrins as visible-light photosensitizers have been extensively utilized in visible-light photocatalysts and photoelectronic materials. So, fabrication of novel porphyrin-based complexes will be benefited for high-efficiency hydrogen evolution and photoelectric response. Here a series of zirconium porphyrin-based coordination complexes were successfully fabricated via a facile two-step strategy. Due to the unique long chain-like structure and low charge-transfer resistance, the zirconium porphyrin-based coordination complexes displayed excellent electrocatalytic performance for hydrogen evolution reaction. The ZrTPP-PTA-1 showed a low overpotential of 60 mV at the current density 10 mA cm−2 and a Tafel slope of 87 mV dec−1 with an ultralow electron transfer resistance of 17.5 Ω. In addition, a quick photocurrent response occurred for these coordination complexes with a visible-light illumination. The photocurrent of the ZrTPP-OA-2 rised up to 2.5 μA under visible-light irradiation. With this pleasant result, these zirconium porphyrin-based coordination complexes have a great potential to become available alternative of current noble electrocatalysts for photoelectric application.

Introduction

Over the past decades, with the rapid development of industrial economy, most of non-renewable resources such as coal, petroleum, natural gas, metallic and nonmetallic ore have been vigorously developed and utilized [1], [2], [3], [4]. However, excessive exploitation of non-regenerative sources has brought us a severe issue of energy shortage [5], [6], [7]. What's worse, the living environment has been extremely polluted due to the vast consumption of coal and oil [8], [9], [10]. Considering the sustainable development, it is urgent and essential to develop more renewable sources [11], [12], [13]. For this reason, many scientists devote themselves to study the devices concerned with the development and utilization of the inexhaustible solar energy and marine resources [14], [15], [16].

Hydrogen is an important and environmentally friendly resource [17], [18], which was regarded as one of the most potential new energy sources instead of fossil fuel [19], [20], [21]. In recent researches, splitting water into hydrogen and oxygen has been considered to be a very promising approach for hydrogen production [22], [23], [24]. Pt is the optimal hydrogen evolution reaction catalyst for the existing discovery [25], [26]. But as a noble metal, Pt metal is available only in small quantities, and only support 10% of the global cars even through all Pt metal in the earth are used in metal-air batteries [27], [28], [29]. Hydrogen production cost by electrochemical water splitting was largely increased due to this situation. Therefore, it is greatly significant to fabricate and develop high-efficiency but also low-cost electrochemical catalysts [30], [31], [32].

Porphyrin with tetra-pyrrole macrocycle is a high-conjugated system, which possess 26 π-electrons and a strong absorption for visible light, and provide a possibility of intermolecular charge transfer as well as delocalization of excitation energy [33], [34], [35], [36]. In addition, the natural features of porphyrins offer preponderance for molecular self-assembly [37], and the π-conjugated central tetra-pyrrole macrocycle in porphyrins can be easily decorated by hydrophobic or hydrophilic radicals, resulting in preparation of porphyrin-based nanomaterials [32], [38]. Because of the tremendous choices of metal nodes and organic linkers, the optical properties of porphyrin MOFs can be engineered. Such unique characteristics, as well as structural predictability and well-defined environments for the skeletons, allow for the use of porphyrin MOFs as optical materials in various fields [32], [37], [38]. From the above, it is no doubt that porphyrins have played an important role in vary fields such as molecular switch, solar cells, simulation of biological photosynthesis, organic electroluminescence, optical storage devices and photoconductive materials [39], [40]. In this paper, a series of long chain-like porphyrin-based coordination complexes were successfully synthesized. Herein, we adopted a novel two-step synthesis method to prepare these coordination complexes. In the first place, the Zr4+ ions were introduced into meso-tetraphenyl porphyrins to generate Zr-porphyrins by coordination bond. In a second step, the Zr-porphyrins were linked via the bridging group of dicarboxylic acid. And at last a long chain-like porphyrin-based coordination complex formed. These coordination complexes showed high-performance for hydrogen evolution reaction, and possessed excellent photoelectric property.

Section snippets

Materials

Meso-Tetraphenyl porphyrin (TPP, 97%), zirconium tetrachloride (ZrCl4), terephthalic acid (PTA), oxalic acid (OA), polyvinyl pyrrolidone (PVP, average mol wt 58,000), polyvinyl pyrrolidone (PVP, average mol wt 1,300,000), N, N-dimethylformamide (DMF), ethanol (97%). All these chemicals were purchased commercially without further purification. The deionized water was obtained from a water purification system.

Preparation of ZrTPP

Meso-Tetraphenyl porphyrin (80 mg, 0.13 mmol) and zirconium tetrachloride (30 mg,

Characterization

The surface morphology was observed by field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM). The SEM images showed that these Zr porphyrin-based coordination complexes presented interlaced long rods or stacked large sheets (Fig. 2a–d). The morphology of ZrTPP-OA-1 and ZrTPP-PTA-1 was similar to the rods, while ZrTPP-OA-2 and ZrTPP-PTA-2 were closer to sheets. The difference between ZrTPP-OA-1or ZrTPP-PTA-1 and ZrTPP-OA-2 or

Conclusions

To sum up, we have successfully fabricated a series of Zr porphyrin-based coordination complexes via a two-step synthetic strategy. The Zr4+ ion coordinated with meso-tetraphenyl porphyrin to form ZrTPP at first, and then the ZrTPP connected with each other via the bridge of dicarboxylic acid to fabricate the long chain-like Zr porphyrin-based coordination complexes. As a sort of electrocatalysts, these Zr porphyrin-based coordination complexes exhibited excellent performance for

Acknowledgments

We gratefully acknowledge financial support from Zhejiang Top Priority Discipline of Textile Science and Engineering, Natural Science Foundation of Zhejiang Province (No. LY13B030009), Science Foundation of Zhejiang Sci-Tech University (ZSTU) (No. 1101820-Y), National Natural Science Foundation of China (No. 21473161 and 21271155).

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