對於水分解電觸媒，貴金屬(如白金)具有最好的效能，但是，它們在地殼中的含量過低會限制其作為觸媒的發展，而為了解決貴金屬電觸媒的問題，在研究材料上會有兩種方向，(一)使用其他的元素材料(二)改進原始材料，因此，本篇論文將報告兩種觸媒材料，奈米紅磷具備磷元素在地殼中高豐富度的優勢，以及研究具有較低貴金屬且具備高活性協同效應的二元材料奈米銻化鉑作為取代白金的觸媒材料。
在這項研究工作中，我們藉由新的膠體合成法合成奈米紅磷以作為不含金屬的電解水產氫觸媒，在地殼中磷的豐富度是鉑的6000倍，奈米紅磷粒徑為246±26 nm，在產氫反應中作為無金屬電觸媒具有出色的活性，由於多數無金屬觸媒需要200-425 mV以達到10 mA cm-2的電流密度，然而奈米紅磷(P-RPNPs)的過電位僅需218 mV即可達到10 mA cm-2的電流密度，與碳材相當且大幅超越塊材(bulk)紅磷。此外，奈米紅磷在循環測試6000 CV掃描和定電壓可持續45小時的過程中也表現出色的耐久性。
在改進原始材料方面，應研究具有較低貴金屬含量的二元過渡金屬材料(binary transition-metal)，二元過渡金屬材料可以通過不同電化學特性的協同整合促進產氫(HER)反應。為了找到針對產氫(HER)反應的高活性材料，Greely團隊模擬了256種不同的二元過渡金屬材料，並預測 PtRu，AsPt，SbPt，BiRh，RhRe，PtRe，AsRu，IrRu，RhRu，IrRe和PtRh具有良好的活性，然而，它們中只有很少的被合成並應用於電催化劑中。在這項研究工作中，我們設計新的膠體合成法合成覆盆子形狀的銻化鉑奈米材料，奈米銻化鉑於電流密度10 mA cm-2 下具有比鉑更低的過電位，僅需27 mV就能達到。在施加0.5 V（vs. RHE）的情況下進行了90000秒的長期耐久性測試，並進行了10000次從0.1 V到-0.5 V（vs. RHE）的循環測試。覆盆子狀銻化鉑（SbPt）奈米粒子的高活性可能歸因於以下兩個原因：(一)具有多個高活性晶面（110），（100），（101）和（012）作為產氫(HER)的反應位置 (二)經由DFT模擬符合的實驗結果，由於Sb 3d軌域的存在加寬了Pt表面的d軌域帶(d-band)，形成促進水分解的協同效應。綜上所述，合成覆盆子狀SbPt的新型膠體合成對奈米材料和奈米結構設計具有重要意義，這項研究可以促進Pt相關材料向HER催化劑的發展。總結，在這項工作中，我們開發了兩種新穎的材料P-RPNPs和SbPt作為前瞻性的電催化觸媒。

For water splitting electrocatalyst, noble metals are usually treated as the first candidate; however, they are hampered by scarcity. In order to solve the problem of precious metal electrocatalysts, we have two methods, using other materials and improving the original materials. Here we mentioned the use of porous red phosphorus nanoparticles, P-RPNPs, as metal-free catalysts with high phosphorus content on earth, and the other binary transition metals with lower noble metal content can be investigated to improve the electrocatalytic activity with synergistic effect.
In this work, we report P-RPNPs synthesized via a new colloidal approach and applied as metal-free electrocatalysts in the hydrogen evolution reaction (HER). The abundance of phosphorus is 6000 times more than Pt. and our material porous RPNPs ranging of 246±26 nm with an outstanding activity as metal-free catalysts in HER with a low overpotential 218 mV to achieve the 10 mA/cm2 current density comparable with carbon material and highly better than red phosphorus. Furthermore, RPNPs exhibited superior long-term durability for cycling tests 6000 CV sweep and static overpotential for 45 hours.
Besides, a binary transition-metal with lower precious metal content should be investigated. Binary transition-metals can facilitate the HER reaction with the synergistic integration of different electrochemical properties. In order to find highly active binary transition-metals toward HER reaction, Greely and co-workers simulated 736 different binary transition-metals including PtRu, AsPt, SbPt, BiRh, RhRe, PtRe, AsRu, IrRu, RhRu, IrRe and PtRh. However, only few of them are synthesized and applied in electrocatalysts. In this work, we report the synthesis of raspberry-like antimony-platinum (SbPt) nanoparticles via a colloidal nanocrystal synthesis. Raspberry-like SbPt nanoparticles exhibited efficient activity with a low overpotential of 27 mV to reach 10 mA cm-2 in acidic media. Long-term durability test was carried out for 90000 seconds with applied 0.5 V (vs. RHE) and cycling tests over 10000 cycles from 0.1 V to -0.5 V (vs. RHE). The high activity of raspberry-like antimony-platinum (SbPt) nanoparticles may be resulted from the following two reasons: (1) Raspberry-like structure SbPt owned versatile active exposed (110), (100), (101), and (012) facets as efficient HER catalyst. (2) As confirmed by both DFT simulation and experimental results, the presence of Sb 3d subsurface broaden the Pt surface d-band, which leads to the synergetic effects for water splitting. To summary, the new colloidal synthesis of raspberry-like SbPt is valuable for nanomaterial and nanostructure design and this study could enhance the development of Pt-related material toward HER catalyst. In this work, we develop two novel electrocatalysts P-RPNPs and SbPt as the promising candidates toward HER.

中文摘要 I
Abstract III
Chapter 1 Porous red phosphorus nanoparticles as metal-free electrocatalyst for hydrogen evolution reaction 1
1.1 Introduction 1
1.2 Experimental Section 3
1.2.1 Chemicals 3
1.2.2 Synthesis of porous red porous red phosphorus nanoparticles 3
1.2.3 Characterization 4
1.2.4 Electrochemical Measurements and Electrode Preparation 5
1.3 Result and discussion 6
1.4 Conclusion 20
Chapter 2 Synthesis of antimony-platinum (SbPt) nanoparticles as highly active electrocatalysts for hydrogen evolution reaction 24
2.1 Introduction 24
2.2 Experimental Section 28
2.2.1 Chemicals 28
2.2.2 Synthesis of intermediate and raspberry-like SbPt nanoparticles 28
2.2.3 Characterization techniques 29
2.2.4 Electrochemical Measurements and Electrode Preparation 29
2.3 Result and discussion 30
2.4 Conclusion 46
Reference 47

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