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Chem 228 Study Guide: Introduction To Solid State Chemistry Structure, Bonding and Two Applications

Chem 228 Study Guide provides an introduction to solid state chemistry, including structure, bonding, and two applications. [1] It discusses the 14 possible unit cell structures and emphasizes the importance of understanding close packing. [2] Key binary compounds like NaCl, CsCl, ZnS, and TiO2 must be drawn and understood at the molecular level. [3] The guide also examines molecular orbitals and band structures in metals, semiconductors, and ionics. Light emitting diodes and photocatalysis are then discussed as two applications, focusing on the use of semiconductors to generate reactive charge carriers upon light absorption that can drive redox chemistry.

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Mohyeddine K. El Sayed
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70 views

Chem 228 Study Guide: Introduction To Solid State Chemistry Structure, Bonding and Two Applications

Chem 228 Study Guide provides an introduction to solid state chemistry, including structure, bonding, and two applications. [1] It discusses the 14 possible unit cell structures and emphasizes the importance of understanding close packing. [2] Key binary compounds like NaCl, CsCl, ZnS, and TiO2 must be drawn and understood at the molecular level. [3] The guide also examines molecular orbitals and band structures in metals, semiconductors, and ionics. Light emitting diodes and photocatalysis are then discussed as two applications, focusing on the use of semiconductors to generate reactive charge carriers upon light absorption that can drive redox chemistry.

Uploaded by

Mohyeddine K. El Sayed
Copyright
© © All Rights Reserved
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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Chem 228 Study Guide: Introduction to Solid State Chemistry

Structure, Bonding and Two Applications

A: Structure and Bonding: Based on Miessler Chapter 7

7 Formulas and Structures:


7.1 Simple Structure
You need to understand what is a “unit cell” in solid state chemistry
There are only 14 unit cells (Check Figure 1)
Three of these are cubic: you need to know these and you need to know which one is close pack.
Two are tetragonal: You need to know.

Close packed structures: We did this in class. You need to know these include tetrahedral and
octahedral holes. Don’t worry about the details of the exact size of the holes, but you need to know the
tetrahedral is smaller than the octahedral.

Figures 7.2 and 7.3 are important, you must know that ABAB close packing gives a hexagonal unit cell,
whereas the ABCABC mode gives the cubic close pack arrangement (unitcell = ccp which is the same as
the fcc unit cell (face centered cubic unit cell)

7-1-2 Structure of Binary Compounds..


You need to know the NaCl, CsCl, ZnS (Figs 7 and 8) and TiO2 (Rutile, Fig 11)) structures in
details. Note that TiO2 can have several polymorphs.. don’t worry about the details, but you need to
know Rutile and Anataze ate two related polymorphs of TiO2.

 This means you should be able to able to draw the solids clearly. For you to do this you must
practice on a white piece paper (similar to the one used in the tests). No one is born with the ability
to draw solid binary compounds. Please check Wikipedia for great description of these three
important solids.

7-3 Molecular Orbitals and Band Structure  Very important)


We covered the idea in class.
You should know how the bands are in metals, semimetals, and ionic compounds
Figures 7.14 and 7.15 give different ways to draw bands.
You should understand what the presentations are about.

B: Two Applications: Light Emitting Diodes and Photocatalysis

Light Emitting Devices


Based on: (i) Miessler section 7.3.1 and
(ii) Handout 1 on Moodle Based on reading from the following website:

http://www.chemistry.wustl.edu/~edudev/LabTutorials/PeriodicProperties/MetalBonding/MetalBondin
g.html

The given reading also includes a large part of the material that we covered pertaining to bonding in
solids. So you should read it carefully.
 The idea here is the design of material that responds by emitting light when exposed to an
external voltage.

 After studying the handout and Missler, you should be able to give a drawing to illustrate the basic
components of an LED. On this drawing you should give a clear advanced description of the chemical
composition of the components and their role in the device. You should know the difference of n-
type and p-type semiconductors and how they are made by doping.

Photocatalysis Using Semiconductors.

1: Akira Fujshima and Kenichi Honda:


Electrochemical Photolysis of Water at a Semiconductor Electrode
Nature volume238, pages37–38
https://www.nature.com/articles/238037a0

This was the first time TiO2 was demonstrated can be useful in photocatalysis.
You need to know the design of the photo-electrochemical cell, and the reaction that takes place at each
electrode.

2: Jiangtian Li and Nianqiang Wu *


Semiconductor-based photocatalysts and photoelectrochemical cells for solar fuel
generation: a review DOI: 10.1039/C4CY00974F (Perspective)
Catal. Sci. Technol., 2015, 5, 1360-1384.
http://pubs.rsc.org/en/content/articlehtml/2015/cy/c4cy00974f

You need to study section 2 carefully. Focus on particulate photocatalysts


(Figure 1a reproduced here). You need to be able to reproduce this figure and
use it to explain the basic idea in photocatalysis using the key terms: (i) light
absorption, (ii) charge separation, (iii) charge migration, (iv) charge
recombination and (v) redox reactions.
 Please go over the intro so you can appreciate what the subject is about.
 Note the part on photoelctrocatalysis (Figure 1b). It is important for you to you to know the idea.

The idea here is to expose semiconductors to light. This generates a hole in the valence band and an electron
in the valence band. The hole can abstract an electron from a chemical, and the electron in the valence band
can reduce another chemical.

In other words, light absorption generates a reactive charge separated species that can do chemistry.

We explained in class that silicon is a semiconductor. Ionic compounds such as NaCl and CsCl are non-
conductors. However, other ionic compounds, especially the oxides and sulfides of transition metal ions can
be semiconductors. The most popular examples are TiO2 and Fe2O3.
Over the past few years chemists designed a large number of synthetic solid semiconductors based on
composite material. The different material has different gaps, and different position of the conduction and
valence bands. They will have therefore different absorption spectra and electrochemistry. See 3 from the
following article. Notice the inclusion of silicon, TiO2 and Fe2O3 in this Table. The different semiconductors can
be used in different redox reactions.
Fig. 3 Band edge positions with respect to the vacuum level and the NHE for selected semiconductors
at pH 0 (a) oxides, phosphates and carbides; (b) chalcogenides and silicon. The top squares represent
the conduction band edges; the bottom squares present the valence band edges. The top numbers
show the exact conduction band level and the number between squares is the band gap. The two
dashed lines indicate the water redox reaction potentials. The data are adapted from ref. 38 with the
permission from the Mineralogical Society of America and modified with the new literature.

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