Polymeric graphitic carbon nitride materials (for simplicity: g-C(3)N(4)) have attracted much attention in recent years because of their similarity to graphene. They are composed of C, N, and some minor H content only. In contrast to graphenes, g-C(3)N(4) is a medium-bandgap semiconductor and in that role an effective photocatalyst and chemical catalyst for a broad variety of reactions. In this Review, we describe the "polymer chemistry" of this structure, how band positions and bandgap can be varied by doping and copolymerization, and how the organic solid can be textured to make it an effective heterogenous catalyst. g-C(3)N(4) and its modifications have a high thermal and chemical stability and can catalyze a number of "dream reactions", such as photochemical splitting of water, mild and selective oxidation reactions, and--as a coactive catalytic support--superactive hydrogenation reactions. As carbon nitride is metal-free as such, it also tolerates functional groups and is therefore suited for multipurpose applications in biomass conversion and sustainable chemistry.

Polymeric Graphitic Carbon Nitride as a Heterogeneous Organocatalyst: From Photochemistry to Multipurpose Catalysis to Sustainable Chemistry

Preface Acknowledgements Notation Part I. Overview and Background Topics: 1. Introduction 2. Overview 3. Theoretical background 4. Periodic solids and electron bands 5. Uniform electron gas and simple metals Part II. Density Functional Theory: 6. Density functional theory: foundations 7. The Kohn-Sham ansatz 8. Functionals for exchange and correlation 9. Solving the Kohn-Sham equations Part III. Important Preliminaries on Atoms: 10. Electronic structure of atoms 11. Pseudopotentials Part IV. Determination of Electronic Structure, The Three Basic Methods: 12. Plane waves and grids: basics 13. Plane waves and grids: full calculations 14. Localized orbitals: tight binding 15. Localized orbitals: full calculations 16. Augmented functions: APW, KKR, MTO 17. Augmented functions: linear methods Part V. Predicting Properties of Matter from Electronic Structure - Recent Developments: 18. Quantum molecular dynamics (QMD) 19. Response functions: photons, magnons ... 20. Excitation spectra and optical properties 21. Wannier functions 22. Polarization, localization and Berry's phases 23. Locality and linear scaling O (N) methods 24. Where to find more Appendixes References Index.

Electronic Structure: Basic Theory and Practical Methods

We have developed an efficient and reliable methodology for crystal structure prediction, merging ab initio total-energy calculations and a specifically devised evolutionary algorithm. This method allows one to predict the most stable crystal structure and a number of low-energy metastable structures for a given compound at any P-T conditions without requiring any experimental input. Extremely high (nearly 100%) success rate has been observed in a few tens of tests done so far, including ionic, covalent, metallic, and molecular structures with up to 40 atoms in the unit cell. We have been able to resolve some important problems in high-pressure crystallography and report a number of new high-pressure crystal structures (stable phases: epsilon-oxygen, new phase of sulphur, new metastable phases of carbon, sulphur and nitrogen, stable and metastable phases of CaCO3). Physical reasons for the success of this methodology are discussed.

Crystal structure prediction using ab initio evolutionary techniques: principles and applications.

First principles calculations were performed to investigate the structural, elastic, and electronic properties of IrN2 for various space groups: cubic Fm-3m and Pa-3, hexagonal P3(2)21, tetragonal P4(2)/mnm, orthorhombic Pmmn, Pnnm, and Pnn2, and monoclinic P2(1)/c. Our calculation indicates that the P2(1)/c phase with arsenopyrite-type structure is energetically more stable than the other phases. It is semiconducting (the remaining phases are metallic) and contains diatomic N-N with the bond distance of 1.414 A. These characters are consistent with the experimental facts that IrN2 is in lower symmetry and nonmetallic. Our conclusion is also in agreement with the recent theoretical studies that the most stable phase of IrN2 is monoclinic P2(1)/c. The calculated bulk modulus of 373 GPa is also the highest among the considered space groups. It matches the recent theoretical values of 357 GPa within 4.3% and of 402 GPa within 7.8%, but smaller than the experimental value of 428 GPa by 14.7%. Chemical bonding and potential displacive phase transitions are discussed for IrN2. For IrN3, cubic skutterudite structure (Im-3) was assumed.

Crystal structures and elastic properties of superhard IrN2 and IrN3 from first principles

In comparing a material's resistance to distort under mechanical load rather than to alter in volume, Poisson's ratio offers the fundamental metric by which to compare the performance of any material when strained elastically. The numerical limits are set by ½ and -1, between which all stable isotropic materials are found. With new experiments, computational methods and routes to materials synthesis, we assess what Poisson's ratio means in the contemporary understanding of the mechanical characteristics of modern materials. Central to these recent advances, we emphasize the significance of relationships outside the elastic limit between Poisson's ratio and densification, connectivity, ductility and the toughness of solids; and their association with the dynamic properties of the liquids from which they were condensed and into which they melt.

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Poisson's ratio and modern materials

Nitrogen usually consists of molecules where two atoms are strongly triple-bonded. Here, we report on an allotropic form of nitrogen where all atoms are connected with single covalent bonds, similar to carbon atoms in diamond. The compound was synthesized directly from molecular nitrogen at temperatures above 2,000 K and pressures above 110 GPa using a laser-heated diamond cell. From X-ray and Raman scattering we have identified this as the long-sought-after polymeric nitrogen with the theoretically predicted cubic gauche structure (cg-N). This cubic phase has not been observed previously in any element. The phase is a stiff substance with bulk modulus >or=300 GPa, characteristic of strong covalent solids. The polymeric nitrogen is metastable, and contrasts with previously reported amorphous non-molecular nitrogen, which is most likely a mixture of small clusters of non-molecular phases. The cg-N represents a new class of single-bonded nitrogen materials with unique properties such as energy capacity: more than five times that of the most powerfully energetic materials.

Single-bonded cubic form of nitrogen

THE temperature distribution in the Earth's core places important constraints on the Earth's internal heat budget and on models of the geodynamo. The solid inner core crystallizes from a liquid outer core, consisting mainly of iron alloyed with a lighter element, at a depth of about 5,100 km (corresponding to a pressure of about 3.3 Mbar). Thus, the most reliable means of determining the temperature gradient in the core is to estimate the melting temperature of iron and iron-rich compounds at the pressure of the inner core boundary. Current estimates range from about 4,000 to 8,000 K; but these estimates, obtained from shock compression1–3, theory (discussed in ref. 4) and extrapolation of static pressure data2,3,5, are poorly constrained. Here I present melting-point measurements on iron and iron–oxygen compounds at static pressures of up to Mbar. Extrapolation of these results to 3.3 Mbar yields a temperature at the inner-core boundary of 4,850±200 K. A weak change in optical absorption observed above 2,000 K may correspond to the solid–solid phase transition found in shock experiments at 2 Mbar (ref. 1).

Temperatures in the Earth's core from melting-point measurements of iron at high static pressures

Silicon nitride (Si3N4) is used in a variety of important technological applications The high fracture toughness, hardness and wear resistance of Si3N4-based ceramics are exploited in cutting tools and anti-friction bearings1; in electronic applications, Si3N4 is used as an insulating, masking and passivating material2 Two polymorphs of silicon nitride are known, both of hexagonal structure: α- and β-Si3N4 Here we report the synthesis of a third polymorph of silicon nitride, which has a cubic spinel structure This new phase, c-Si3N4, is formed at pressures above 15 GPa and temperatures exceeding 2,000 K, yet persists metastably in air at ambient pressure to at least 700 K First-principles calculations of the properties of this phase suggest that the hardness of c-Si3N4 should be comparable to that of the hardest known oxide (stishovite3, a high-pressure phase of SiO2), and significantly greater than the hardness of the two hexagonal polymorphs

Synthesis of cubic silicon nitride

The interpretation of seismic data and computer modeling requires increased accuracy in relevant material properties in order to improve our knowledge of the structure and dynamics of the Earth's deep interior. To obtain such properties, a complementary method to classic shock compression experiments and theoretical calculations is the use of laser-heated diamond cells, which are now producing accurate data on phase diagrams, equations of state, and melting. Data on one of the most important measurements, the melting temperatures of iron at very high pressure, are now converging. Two other issues linking core properties to those of iron are investigated in the diamond cell: One is the melting point depression of iron in the presence of light elements, and the other is the structure of iron at the conditions of the inner core. First measurements on eutectic systems indicate a significant decrease in the melting point depression with increasing pressure, which is in contrast to previous predictions. X-ray diffraction measurements at simultaneously high pressure and high temperature have improved significantly with the installation of high-pressure “beam lines” at synchrotron facilities, and structural measurements on iron are in progress. Considerable efforts have been made to develop new techniques to heat minerals at the conditions of the deep mantle in the diamond cell and to measure their phase relations reliably. Even measurements of the melting behavior of realistic rock compositions at high pressure, previously considered to be impossible in the diamond cell, have been reported. The extrapolated solidus of the lower mantle intersects the geotherm at the core-mantle boundary, which may explain the seismically observed ultra low velocity zone. The diamond cell has great potential for future development and broad application, as new measurements on high-pressure geochemistry at deep mantle and core conditions have opened a new field of research. There are, however, strict experimental requirements for obtaining reliable data, which are summarized in the present paper. Results from recent measurements of melting temperatures and phase diagrams of lower mantle and core materials at very high pressure are reviewed.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/1998RG000053

High pressure experiments and the phase diagram of lower mantle and core materials

The pressure dependence of the thermal expansion coefficient, α, previously reported as (∂lnα/∂lnV)T = 5.5 ± 0.5 by Chopelas and Boehler [1989] is refined, using systematics in the volume dependence of (∂T/∂P)s measured for a large number of materials at high pressures and high temperatures. Since (∂ln (∂T/∂P)s/∂(V/V0))T is found to be constant and material independent over a very large compression range, (∂lnα/∂lnV)T is proportional to the compression, V/V0. We find α decreases by a factor of 5 for MgO throughout the mantle, reaching a value of 1.0 · 10−5 K−1 at its bottom. Densities of perovskite (PV) and magnesiowustite (MW) are calculated for lower mantle conditions using our new α(P, T), a room temperature finite strain equation, and recent data on the Mg-Fe partitioning in the PV-MW system. Both minerals have nearly identical densities to those of PREM throughout the entire lower mantle, which allows variable PV:MW ratios. A lower mantle made entirely of PV with a molar ratio of Mg:Fe of 88:12 would be about 0.11 g/cm3 or 2.5% denser than this mixture, but this density would just be within the uncertainty in PREM. A change in chemistry at 660 km depth to a PV mantle requires a thermal boundary which would improve the match in the densities between PV and PREM. These density agreements therefore preclude evaluation of a mineralogical model for the lower mantle using density comparisons. Recent measurements on melting of Fe, FeO, and FeS, however, suggest temperatures at the core-mantle boundary below 3500 K, which tends to favor a geotherm without a large thermal boundary at 660 km depth.

Reinhard Boehler

Papers

Single-bonded cubic form of nitrogen

Temperatures in the Earth's core from melting-point measurements of iron at high static pressures

Synthesis of cubic silicon nitride

High pressure experiments and the phase diagram of lower mantle and core materials

Thermal expansivity in the lower mantle