Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.

Noble metal-free hydrogen evolution catalysts for water splitting

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.

https://faculty.missouri.edu/~glaserr/3700s15/Cocats_ar300227e.pdf

Roles of cocatalysts in photocatalysis and photoelectrocatalysis.

A review on g-C3N4-based photocatalysts

Photocatalytic water splitting represents a promising strategy for clean, low-cost, and environmental-friendly production of H2 by utilizing solar energy. There are three crucial steps for the photocatalytic water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic H2 and O2 evolution reactions. While significant achievement has been made in optimizing the first two steps in the photocatalytic process, much less efforts have been put into improving the efficiency of the third step, which demands the utilization of cocatalysts. To date, cocatalysts based on rare and expensive noble metals are still required for achieving reasonable activity in most semiconductor-based photocatalytic systems, which seriously restricts their large-scale application. Therefore, seeking cheap, earth-abundant and high-performance cocatalysts is indispensable to achieve cost-effective and highly efficient photocatalytic water splitting. This review for the first time summarizes all the developed earth-abundant cocatalysts for photocatalytic H2- and O2-production half reactions as well as overall water splitting. The roles and functional mechanism of the cocatalysts are discussed in detail. Finally, this review is concluded with a summary, and remarks on some challenges and perspectives in this emerging area of research.

Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting

WS2/CdS photocatalysts with different amounts of WS2 cocatalyst are prepared by loading WS2 on CdS with an impregnation–sulfidation approach. The transformation process of the tungsten species loaded on CdS together with the junctions formed between WS2 and CdS are clearly demonstrated with X-ray photoelectron spectroscopy and transmission electron microscopy. Photocatalytic H2 production on WS2/CdS catalysts under visible light (λ > 420 nm) shows that WS2 cocatalyst plays a crucial role in H2 production. Under optimum conditions, the rate of H2 evolution can be increased by up to 28 times when CdS was loaded with only 1.0 wt % WS2, and WS2 demonstrates a catalytic performance comparable or even superior to those of noble metals. Photocatalytic reaction results and electrochemical measurements indicate that the significantly enhanced H2 evolution of WS2/CdS catalyst mainly owns to the junctions formed between WS2 and CdS and the excellent performance of WS2 as a cocatalyst in catalyzing H2 evolution.

Photocatalytic H2 Evolution on CdS Loaded with WS2 as Cocatalyst under Visible Light Irradiation

The oxygen evolution is kinetically the key step in the photocatalytic water splitting. Cocatalysts could lower the activation potential for O2 evolution. However, the cocatalyst for O2 evolution has been less investigated, and few effective cocatalysts were reported. This paper reports that the O2 evolution rate of photocatalytic water splitting under visible light irradiation can be significantly enhanced when the electrocatalyst cobalt–phosphate (denoted as CoPi) was deposited on BiVO4. The photocurrent density is also greatly enhanced by loading CoPi on BiVO4 electrode, and this enhancement in performance shows the similar trend between the photocatalytic activity and photocurrent density. We also found that this tendency is true for BiVO4 loaded with a series of different electrocatalysts as the cocatalysts. These results demonstrate that an effective electrocatalyst of water oxidation can be also an effective cocatalyst for O2 evolution from photocatalytic water oxidation. By depositing the CoPi as ...

Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation Cocatalyst: Essential Relations between Electrocatalyst and Photocatalyst

Photoelectrochemical (PEC) water splitting is an ideal approach for renewable solar fuel production. One of the major problems is that narrow bandgap semiconductors, such as tantalum nitride, though possessing desirable band alignment for water splitting, suffer from poor photostability for water oxidation. For the first time it is shown that the presence of a ferrihydrite layer permits sustainable water oxidation at the tantalum nitride photoanode for at least 6 h with a benchmark photocurrent over 5 mAcm(-2), whereas the bare photoanode rapidly degrades within minutes. The remarkably enhanced photostability stems from the ferrihydrite, which acts as a hole-storage layer. Furthermore, this work demonstrates that it can be a general strategy for protecting narrow bandgap semi-conductors against photocorrosion in solar water splitting.

A Tantalum Nitride Photoanode Modified with a Hole-Storage Layer for Highly Stable Solar Water Splitting

The photocatalytic activity and stability of nanocrystals (NCs) are two important issues for their application in photocatalysis. In this work, we report a combined method to promote the photocatalytic activity as well as the stability of CdS NCs for photocatalytic H2 evolution. ZnS shell was grown on CdS NCs forming type I core/shell CdS/ZnS nanocrystals (NCs) to restrain the photocorrosion and passivate the trap states on CdS NCs. Thereafter, dual cocatalysts were loaded to promote the separation and transfer of electrons and holes from the core to outer surface for photocatalytic reactions. It is found that Pt and Ni are effective reduction cocatalysts (RCs) while PdS and PbS are effective oxidation cocatalysts (OCs) for promoting the charge separation and transfer. This strategy was also proved to be effective for other type I core/shell NCs, such as CdTe/CdS/ZnS NCs.

Dual Cocatalysts Loaded Type I CdS/ZnS Core/Shell Nanocrystals as Effective and Stable Photocatalysts for H2 Evolution

The photoanodes with heterojunction behavior could enable the development of solar energy conversion, but their performance largely suffers from the poor charge separation and transport process through the multiple interfacial energy levels involved. The question is how to efficiently manipulate these energy levels. Taking the n-Si Schottky photoanode as a prototype, the undesired donor-like interfacial defects and its adverse effects on charge transfer in n-Si/ITO photoanode are well recognized and diminished through the treatment on electronic energy level. The obtained n-Si/TiOx/ITO Schottky junction exhibits a highly efficient charge transport and a barrier height of 0.95 eV, which is close to the theoretical optimum for n-Si/ITO Schottky contact. Then, the holes extraction can be further facilitated through the variation of surface energy level, with the NiOOH coated ITO layer. This is confirmed by a 115% increase in surface photovoltage of the photoanodes. Eventually, an unprecedentedly low onset po...

Jingfeng Han

Papers

Photocatalytic H2 Evolution on CdS Loaded with WS2 as Cocatalyst under Visible Light Irradiation

Photocatalytic Water Oxidation on BiVO4 with the Electrocatalyst as an Oxidation Cocatalyst: Essential Relations between Electrocatalyst and Photocatalyst

A Tantalum Nitride Photoanode Modified with a Hole-Storage Layer for Highly Stable Solar Water Splitting

Dual Cocatalysts Loaded Type I CdS/ZnS Core/Shell Nanocrystals as Effective and Stable Photocatalysts for H2 Evolution

Manipulating the Interfacial Energetics of n-type Silicon Photoanode for Efficient Water Oxidation.