Shaohua Shen

Bio: Shaohua Shen is an academic researcher from Xi'an Jiaotong University. The author has contributed to research in topics: Water splitting & Photocatalysis. The author has an hindex of 58, co-authored 189 publications receiving 15145 citations. Previous affiliations of Shaohua Shen include Lawrence Berkeley National Laboratory & University of California, Berkeley.

Semiconductor-based Photocatalytic Hydrogen Generation

Abstract: 2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Filling the oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting

Abstract: It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Co3O4 has been developed as a highly efficient OER electrocatalyst, but it has almost no activity for HER. In a previous study, it has been demonstrated that the formation of oxygen vacancies (VO) in Co3O4 can significantly enhance the OER activity. However, the stability of VO needs to be considered, especially under the highly oxidizing conditions of the OER process. It is a big challenge to stabilize the VO in Co3O4 while reserving the excellent activity. Filling the oxygen vacancies with heteroatoms in the VO-rich Co3O4 may be a smart strategy to stabilize the VO by compensating the coordination numbers and obtain an even surprising activity due to the modification of electronic properties by heteroatoms. Herein, we successfully transformed VO-rich Co3O4 into an HER-OER electrocatalyst by filling the in situ formed VO in Co3O4 with phosphorus (P-Co3O4) by treating Co3O4 with Ar plasma in the presence of a P precursor. The relatively lower coordination numbers in VO-Co3O4 than those in pristine Co3O4 were evidenced by X-ray adsorption spectroscopy, indicating that the oxygen vacancies were created after Ar plasma etching. On the other hand, the relatively higher coordination numbers in P-Co3O4 than those in VO-Co3O4 and nearly same coordination number as that in pristine Co3O4 strongly suggest the efficient filling of P in the vacancies by treatment with Ar plasma in the presence of a P precursor. The Co–O bonds in Co3O4 consist of octahedral Co3+(Oh)–O and tetrahedral Co2+(Td)–O (Oh, octahedral coordination by six oxygen atoms and Td, tetrahedral coordination by four oxygen atoms). More Co3+(Oh)–O are broken when oxygen vacancies are formed in VO-Co3O4, and more electrons enter the octahedral Co 3d orbital than those entering the tetrahedral Co 3d orbital. Then, with the filling of P in the vacancy site, electrons are transferred out of the Co 3d states, and more Co2+(Td) than Co3+(Oh) are left in P-Co3O4. These results suggest that the favored catalytic ability of P-Co3O4 is dominated by the Co2+(Td) site. P-Co3O4 shows superior electrocatalytic activities for HER and OER (among the best non-precious metal catalysts). Owing to its superior efficiency, P-Co3O4 can directly catalyze overall water splitting with excellent performance. The theoretical calculations illustrated that the improved electrical conductivity and intermediate binding by P-filling contributed significantly to the enhanced HER and OER activity of Co3O4.

Boron-doped nitrogen-deficient carbon nitride-based Z-scheme heterostructures for photocatalytic overall water splitting

Abstract: Photocatalytic overall water splitting can be achieved using Z-scheme systems that mimic natural photosynthesis by combining dissimilar semiconductors in series. However, coupling well-suited H2- and O2-evolving components remains challenging. Here, we fabricate a Z-scheme system for photocatalytic overall water splitting based on boron-doped, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets. We prepare ultrathin carbon nitride nanosheets with varying levels of boron dopants and nitrogen defects, which leads to nanosheets that can act as either H2- or O2-evolving photocatalysts. Using an electrostatic self-assembly strategy, the nanosheets are coupled to obtain a 2D/2D polymeric heterostructure. Owing to their ultrathin nanostructures, strong interfacial interaction and staggered band alignment, a Z-scheme route for efficient charge-carrier separation and transfer is realized. The obtained heterostructure achieves stoichiometric H2 and O2 evolution in the presence of Pt and Co(OH)2 co-catalysts, and the solar-to-hydrogen efficiency reaches 1.16% under one-sun illumination. Splitting water using suspensions of particulate carbon nitride-based photocatalysts may be a cheap way to produce hydrogen, but efficiencies have remained low. Now, Shen and colleagues use doped carbon nitride-based Z-scheme heterostructures to split water with a solar-to-hydrogen efficiency of 1.1% in the presence of metal-based co-catalysts.

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution.

Abstract: Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C3 N4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C3 N4 . The resultant boron-doped and nitrogen-deficient g-C3 N4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h-1 g-1 , much higher than previously reported g-C3 N4 . It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g-C3 N4 , the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C-N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g-C3 N4 with simultaneous introduction of dopants and defects for high-performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.

Hematite heterostructures for photoelectrochemical water splitting: rational materials design and charge carrier dynamics

Abstract: Hematite (α-Fe2O3), with a bandgap suitable for absorption of the solar spectrum, is ideally suited for use as a photoanode material in photoelectrochemical (PEC) conversion of solar light into hydrogen fuel via water splitting. However, low hole mobility, short hole lifetime, high density of surface states, and slow kinetics for oxygen evolution at the α-Fe2O3/electrolyte interface have limited the PEC performance of α-Fe2O3 photoanodes to date. Along with numerous reports on doping and nanostructuring of α-Fe2O3, increased attention has been paid to α-Fe2O3 heterostructure design for improved PEC performance. This review article provides an overview of four main approaches to rational heterostructure design: coupling α-Fe2O3 with (1) an n- or p-type semiconductor for promoting charge separation; (2) a nanotextured conductive substrate for efficient charge collection; (3) a surface/interface passivation layer for reduced surface/interface charge recombination; (4) a catalyst for accelerated water oxidation kinetics. The achievements to date demonstrate that high PEC performance may be accessed with these designs. In addition, we review time-resolved laser techniques used to probe the charge carrier dynamics of these heterostructures. Dynamic studies have provided insight into the mechanisms responsible for the improved PEC performance in these materials and helped to guide continued design of α-Fe2O3 heterostructures for further enhancement of PEC water splitting. As summarized in this review article, rational heterostructure design is a promising strategy to push forward the application of α-Fe2O3 for potential low cost and high efficiency solar hydrogen conversion. A better fundamental understanding of the charge carrier dynamics in these structures in turn helps to guide and improve the heterostructure design.

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Semiconductor-based Photocatalytic Hydrogen Generation

Abstract: 2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals

Abstract: When used as a photocatalyst, titanium dioxide (TiO(2)) absorbs only ultraviolet light, and several approaches, including the use of dopants such as nitrogen, have been taken to narrow the band gap of TiO(2). We demonstrated a conceptually different approach to enhancing solar absorption by introducing disorder in the surface layers of nanophase TiO(2) through hydrogenation. We showed that disorder-engineered TiO(2) nanocrystals exhibit substantial solar-driven photocatalytic activities, including the photo-oxidation of organic molecules in water and the production of hydrogen with the use of a sacrificial reagent.

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

Abstract: 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...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

Abstract: 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...