There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many strategies have been developed in the past few decades and the most widely used one is to develop photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction and the multicomponent heterojunction. The photocatalytic properties of the four junction systems are also discussed in relation to the environmental and energy applications, such as degradation of pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a summary and some perspectives on the challenges and new directions in this exciting and still emerging area of research.

Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances

Semiconductor-based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g-C3N4) for visible-light photocatalytic water splitting, g-C3N4 -based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g-C3N4 -based photocatalysts, including the fabrication and nanostructure design of pristine g-C3N4 , bandgap engineering through atomic-level doping and molecular-level modification, and the preparation of g-C3N4 -based semiconductor composites. Also, the photo-catalytic applications of g-C3N4 -based photocatalysts in the fields of water splitting, CO2 reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non-noble-metal cocatalysts, and Z-scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g-C3N4 -based photocatalysts are highlighted.

Polymeric Photocatalysts Based on Graphitic Carbon Nitride

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.

Charge separation is crucial for increasing the activity of semiconductor-based photocatalysts, especially in water splitting reactions. Here we show, using monoclinic bismuth vanadate crystal as a model photocatalyst, that efficient charge separation can be achieved on different crystal facets, as evidenced by the reduction reaction with photogenerated electrons and oxidation reaction with photogenerated holes, which take place separately on the {010} and {110} facets under photo-irradiation. Based on this finding, the reduction and oxidation cocatalysts are selectively deposited on the {010} and {110} facets respectively, resulting in much higher activity in both photocatalytic and photoelectrocatalytic water oxidation reactions, compared with the photocatalyst with randomly distributed cocatalysts. These results show that the photogenrated electrons and holes can be separated between the different facets of semiconductor crystals. This finding may be useful in semiconductor physics and chemistry to construct highly efficient solar energy conversion systems.

/pdf/spatial-separation-of-photogenerated-electrons-and-holes-396qh4w4yc.pdf

Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO4

Cocatalysts play important roles in promoting the catalytic reactions of semiconductor photocatalysts. Especially, deposition of dual cocatalysts, i.e., oxidation and reduction cocatalysts, onto a semiconductor photocatalyst can significantly improve its photocatalytic activity due to the synergetic effect of rapid consumption of photogenerated electrons and holes. However, in most cases, the cocatalysts are randomly deposited onto the semiconductor photocatalysts, where the cocatalysts cannot function fully. Herein, based on the findings that photogenerated electrons and holes can be spatially separated onto the different facets of BiVO4, we have successfully prepared two types of photocatalysts (M/MnOx/BiVO4 and M/Co3O4/BiVO4, where M stands for noble metals) with reduction and oxidation cocatalysts selectively deposited onto the {010} and {110} facets of BiVO4 by a photo-deposition method. Remarkably enhanced photocatalytic activities were observed for such assembled photocatalysts in control experiments of photocatalytic water oxidation and photocatalytic degradation of methyl orange and rhodamine B. In-depth investigations show that the enhanced photocatalytic performances are due to not only the intrinsic nature of charge separation between the {010} and {110} facets of BiVO4, but also the synergetic effect of dual-cocatalysts deposited onto the different facets of BiVO4. This work further proves the feasibility of the general concepts for approaching efficient artificial photosynthesis systems, namely, engineering of crystal-based photocatalysts by selective deposition of suitable reduction and oxidation cocatalysts onto the different facets of light absorbing semiconductor crystals.

Highly efficient photocatalysts constructed by rational assembly of dual-cocatalysts separately on different facets of BiVO4

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

Monoclinic BiVO(4) crystals with preferentially exposed (040) facets were hydrothermally synthesized by using a trace amount of TiCl(3) as the directing agent; this function was confirmed by X-ray diffraction patterns (XRD) and high-resolution transmission electron microscopy (HRTEM). The effects of the directing agent TiCl(3) and the pH values applied during synthesis have been studied, and the optimized BiVO(4) sample with highly exposed (040) facet could be obtained by using 1.2 at.% of TiCl(3) as the directing agent at a pH value of 2. Some complementary techniques were also applied to exclude the effects of the structural and physical property changes, such as surface area and hydrophilicity. The photocatalytic activity of oxygen evolution on BiVO(4) is found to be proportionally correlated with the exposed surfaces of the (040) facet. It is assumed that the active sites with a BiV(4) structure on the exposed (040) facet is assigned to be responsible for the high activity of O(2) evolution.

Donge Wang

Papers

Roles of cocatalysts in photocatalysis and photoelectrocatalysis.

Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO4

Highly efficient photocatalysts constructed by rational assembly of dual-cocatalysts separately on different facets of BiVO4

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

Crystal Facet Dependence of Water Oxidation on BiVO4 Sheets under Visible Light Irradiation