VIPEr

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Course Level:

Corequisites:

Prerequisites:

Topics Covered:

Related activities:

Visualizing solid state structures using CrystalMaker generated COLLADA files

Solid State Models with ICE Solid State Model Kits

Solid State Stoichiometry Online

X-ray Crystallography

Close Packing Activity

Introduction to Miller Indices

Implementation Notes:

This learning object was developed at the 2017 MARM IONiC workshop on VIPEr and Literature Discussions. It has not yet been implemented.

This could be assigned for homework, but would likely work better in class with guidance.

Time Required:

This will probably take 50 minutes depending on how much work with models you do.

Web Resources:

J. Am. Chem. Soc. 2016, 138, 471-474

3 Jun 2017

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Submitted by Janet Schrenk, University of Massachusetts Lowell

Additional Authors:

Barbara Reisner, James Madison University

Catherine McCusker, East Tennessee State University

Eric Villa, Creighton University

Meng Zhou, Lawrence Technological University

Evaluation Methods:

Evaluation methods are at the discretion of the instructor. For example, you may ask students to provide written answers to the questions, evaluate whether they participated in class discussion, or ask students to present their answers to specific questions to the class.

Description:

In this literature discussion, students use a paper from the literature to explore the synthesis, structure, characterization (powder XRD, EDS and TEM) and energetics associated with the production of a metastable wurtzite CoS phase. Students also are asked define key terms and acronyms used in the paper; identify the goal of the experiments and determine if the authors met their goal. They examine the fundamental concepts around the key crystal structures available.

Preserving Both Anion and Cation Sublattice Features during a Nanocrystal Cation-Exchange Reaction: Synthesis of a Metastable Wurtzite-Type CoS and MnS

Powell, A.E., Hodges J.M., Schaak, R.E. J. Am. Chem. Soc. 2016, 138, 471-474.

http://pubs.acs.org/doi/abs/10.1021/jacs.5b10624

There is an in class activitiy specifically written for this paper.

Corequisites:

Course Level:

Topics Covered:

Electronic spectroscopy

Extended structure

Kinetics

Reaction mechanisms

Thermodynamics

Prerequisites:

General Chemistry

Learning Goals:

In answering these questions, a student will be able to…

define important scientific terms and acronyms associated with the paper;
describe the rocksalt, NiAs, wurtzite, and zinc blende in terms of anion packing and cation coordination;
differentiate between the structure types described in the paper;
explain the difference between thermodynamically stable and metastable phases and relate it to a free energy diagram; and
describe the structural and composition information obtained from EDS, powder XRD, and TEM experiments.

Subdiscipline:

Investigating the structures of close packed solids in metal sulfide nanocrystals

Related activities:

Thinking about Mechanisms of Metal Ion Exchange

Solid State Models with ICE Solid State Model Kits

Visualizing solid state structures using CrystalMaker generated COLLADA files

Solid State Stoichiometry Online

X-ray Crystallography

Close Packing Activity

Introduction to Miller Indices

Implementation Notes:

This learning object was created at the 2017 IONiC Workshop on VIPEr and Literature Discussion. It has not yet been used in class.

Time Required:

50 minutes

Web Resources:

J. Am. Chem. Soc. 2016, 138, 471-474

3 Jun 2017

Quantum Dot Growth Mechanisms

Submitted by Chi Nguyen, United States Military Academy

Additional Authors:

Brian Smith, Bucknell University

Kate Plass, Franklin & Marshall College

Roxy Swails, Lafayette College

Evaluation Methods:

The question document attempted by students in preparation for the literature discussion will be due prior to the in-class discussion. In particular, students' performance on the particle-in-a-box question will be evaluated to assess retention from the previously covered course material. The next exam following the discussion will contain specific question(s) (data/figure analysis) addressing these topics. Students' performance difference between the two will be evaluated. The extent to which students improve their post-discussion understanding of the concepts will direct future implementation.

Evaluation Results:

To be determined. This is a newly proposed literature discussion.

Description:

This literature article covers a range of topics introduced in a sophomore level course (confinement/particle-in-a-box, spectroscopy, kinetics, mechanism) and would serve as a an end-of-course integrated activity, or as a review activity in an upper level course. The authors of the article employ UV-vis absorption spectroscopy of CdSe quantum dots as a tool to probe the growth mechanism of the nanoparticles, contrasting two pathways.

Reference: DOI 10.1021/ja3079576 J. Am. Chem. Soc. 2012, 134, 17298-17305

Corequisites:

Course Level:

Topics Covered:

Electronic spectroscopy

Electronic structure

Kinetics

Physical properties

Reaction mechanisms

Prerequisites:

General Chemistry

Learning Goals:

Apply the particle in a box model to interpret absorbance spectra with respect to nanoparticle size.

Analyze the step-growth and living chain-growth mechanisms proposed in this paper.

Evaluate the kinetics as it applies to the step-addition.

Recognize and apply multiple scientific concepts in an integrative manner.

Subdiscipline:

Building hybrid nanoparticles

Related activities:

Colloidal Hybrid Nanoparticles

Education Resources at Beloit College - Materials Chemistry, Nanoscience and Solid State Chemistry

Materials Chemistry course

Band Structures, Electronic and Optical Properties of Metals, Semiconductors, and Insulators

Inorganic Chemistry Spectroscopy Tutorial: Theoretical Principles and Applications

Implementation Notes:

Sophomore level implementation: Recommend focusing on select portions (e.g. Figures 1b, 2, 5 with corresponding text) of the paper rather than having students read the entire document. The learning objects focus on select topics, such as particle-in-a-box, reaction mechanism, and kinetics in conjunction with absorbance spectroscopy. This would be a good literature discussion resource for an end-of-course integrative experience that encompasses multiple topics from general chemistry and inorganic chemistry.

Advance level implementation: For an upper division course, incorporate the paper in its entirety early in the course as an assessment on students’ ability to integrate multiple concepts that they should have learned in general chemistry, organic chemistry, and physical chemistry. To enhance the experience, accompanying the literature discussion on this paper with a laboratory experience by repeating the experimental and characterization procedures presented in the paper, and having students' compare their results with published results. This also serves to enhance students’ scientific literacy by critically assessing the quality of the paper.

Excerpts of the paper and questions can be used on a graded event, or as lesson preparation for in class discussion.

Time Required:

In-class discussion takes approximately 50 minutes with students having already read the paper and submitted their responses to the questions.

Web Resources:

J. Am. Chem. Soc. 2012, 134, 17298-17305

27 Mar 2017

Nanomaterials for Carbon Dioxide Reduction

Submitted by Anne Bentley, Lewis & Clark College

Evaluation Methods:

The problems presented here represented half the points on the final exam – I have included point totals to give an idea of the weight assigned to each problem.

Evaluation Results:

Twelve students were enrolled in my course in the fall 2016. The average overall score for these problems was 78%.

For problem 1b, I calculated the oxidation numbers using the familiar general chemistry method of assigning oxygen as –2 and hydrogen as +1. Students recently coming through organic may have some other way to do it, and you may need to provide directions for your students about your preferred method. I think I could have worded part (c) better to try to emphasize the redox processes involved. I wanted them to think of combustion, but I think they needed to be specifically prompted, such as "Give an example of the combustion processes that generate CO2 and trace the oxidation state of carbon through the reaction." Overall my students scored 86% on problem 1.

The second problem (about another method that could be used to measure d-spacing) was fairly hit or miss. Five students got full credit, six students got 3 points, and one got zero. Eleven out of twelve did answer part (a) correctly. I realized as I made this LO that the article says the carbon-based material doesn’t diffract X-rays, but doesn’t actually directly explain whether or not the Cu nanoparticles diffracted X-rays, so you may need to adjust the question to be technically accurate.

Question three (re: surfactants in nanoparticle synthesis) referred back to knowledge from earlier in the course. The overall score was 61%.

Question 4 (define and describe electrodes) was fairly straightforward, and students scored 85%.

Question 5 caused some confusion, as some students missed that I was looking for “carbon-containing” products only. I didn’t count off for that mistake, but it made the problem harder for students who included hydrogen in each box. Overall, students did very well on this problem (89% correct).

Question 6 – again, not too much trouble here (84% correct).

Question 7 – I was surprised that students didn’t do better on this question, as I thought that water reduction was mentioned often in the article. Only three (of 12) students scored 5 points on this problem, and the average score was 53%. This was probably my favorite question, as it foreshadows electrochemistry topics I cover in my inorganic course.

Description:

This literature discussion is based on an article describing the use of copper nanoparticles on an N-doped textured graphene material to carry out the highly selective reduction of CO₂ to ethanol (Yang Song et al., “High-Selectivity Electrochemical Conversion of CO₂ to Ethanol using a Copper Nanoparticle / N-Doped Graphene Electrode” ChemistrySelect 2016, 1, 6055-6061. DOI: 10.1002/slct.201601169). The article provides a good introduction to the concepts of electrochemical reduction, selectivity and recycling of fossil fuels. The literature discussion assignment shared here was used as half of the final exam in a half-credit nanomaterials chemistry course, but could be adapted for use as a take-home or in-class assignment.

Topics Covered:

Chemical literature

Electron transfer

Corequisites:

Prerequisites:

Course Level:

Learning Goals:

After reading this paper and working through the problems, a student will be able to:

assign oxidation states to carbon and trace the oxidation and reduction of carbon through fossil fuel combustion and CO₂ conversion
describe the role of control experiments in studying the CO₂ conversion presented in the article
define the word “selective” in the context of this research
use the proposed mechanism to explain why the electrode studied produces ethanol in such a high proportion
identify the primary reaction competing with CO₂ reduction for available electrons

Subdiscipline:

Electrochemistry

Main Group Chemistry

Kinetics of electrocatalytic reduction of carbon dioxide by Mn catalysts containing bulky bipyridine ligands

Related activities:

Recyclable Catalyst for Conversion of Carbon Dioxide into Formate Attributable to an Oxyanion on the Catalyst Ligand

Dissecting Catalysts for Artificial Photosynthesis

Implementation Notes:

These questions comprised half of the final exam for my half-credit nanomaterials chemistry course in the fall of 2016. I gave the article to the students one week ahead of time. They were encouraged to read the article, make any small notes they liked, and meet with me in office hours with questions. At the final exam they were allowed to use their copy of the article, but they were also required to hand in their copy with their exam so that I could make sure they hadn't written lots of extraneous information on the exam copy.

The nanomaterials course features near-weekly homework assignments centered around articles from the literature. Because I used this article at the end of the course, students were already familiar with nanomaterials synthesis and characterization techniques. Thus, some of the questions I asked relied on previous knowledge.

Please feel free to adapt these questions and add some of your own. Leave comments describing any new questions you’ve added.

Time Required:

one hour

Web Resources:

Link to article

23 Mar 2016

Nanomaterials Chemistry

Submitted by Anne Bentley, Lewis & Clark College

This list includes a number of LOs to help in teaching nanomaterials subjects; however, it is not exhaustive.

Updated June 2018.

Subdiscipline:

Atomic Structure and Periodicity

Electrochemistry

Bonding models: Extended systems

Topics Covered:

Physical properties

Prerequisites:

No Prerequisites

Corequisites:

Education Resources at Beloit College - Materials Chemistry, Nanoscience and Solid State Chemistry

Learning Objects:

Exploring the Nanoworld Innovating through Materials from the University of Wisconsin Madison

Solid state, Semiconductors, Electrochemistry, and Nanowires for Solar Cells

Copper Oxide Crystal Growth

Introduction to Miller Indices

Zeolite Synthesis

Visualization of Zeolite Structure

Preparation of a Ferrofluid

Fe2GeS4 Nanocrystals for Photovoltaics

Brief introduction to local surface plasmons (LSPRs) for nanoparticle color

Colloidal Hybrid Nanoparticles

Building hybrid nanoparticles

Defining Crystalline/Amorphous Phases of Nanoparticles through X-ray Absorption Spectroscopy and X-ray Diffraction: The Case of Nickel Phosphide

A Schaaking development of colloidal hybrid nanoparticles

Tuning the band gap of CZT(S,Se) nanocrystals by anion substitution

Concept mapping the primary literature: "Compositionally Tunable Cu2ZnSn(S1-x,Sex)4 nanocrystals"

Synthesis and Characterization of Magnetic Spinel Nanoparticles

Effects of defects on the properties of single-walled carbon nanotubes

Synthesis of Zinc Oxide Nanoparticles and Characterization by Powder X-ray Diffraction

Sol-Gel Silica: Nanoarchitectures of Being and Nothingness

Investigating the structures of close packed solids in metal sulfide nanocrystals

An ion exchange method to produce metastable wurtzite metal sulfide nanocrystals

Quantum Dot Growth Mechanisms

Nanomaterials for Carbon Dioxide Reduction

Introduction to the Synthesis and Properties of Nanoparticles

Course Level:

First year

Second year

Upper Division

29 Jun 2015

Copper Oxide Crystal Growth

Submitted by Ellen Steinmiller, University of Dallas

Evaluation Methods:

Student answers to the reading comprehension questions were collected at the beginning of class and graded out of 10 points. An additional 15 points was based on on class participation during the discussion and answers to the in class questions.

Evaluation Results:

Overall, students did well on this paper. During the group problems, students struggled the most with Miller indexes and drawing the layer diagrams of the Cu atoms. In the future I would incorporate ICE models in the class discussion so that students can more clearly see the different crystal planes. Students are often quite confused as to why copper oxide is a primitive cubic cell and I think see the models would help with the visualization that not all Cu atoms are created equally.

Description:

Students in a 2^nd year inorganic class read an article describing the effect of additives on the final morphology of copper oxide. (Siegfried, M.J., and Choi, K-S, “Elucidating the Effect of Additives on the Growth and Stability of Cu₂O Surfaces via Shape Transformation of Pre-Grown Crystals”J. Am. Chem. Soc., 2006, 128 (32), pp 10356–10357. dx.doi.org/10.1021/ja063574y). The authors describe a systematic method that exploits the preferential adsorption phenomenon to regulate crystals shapes by observing the shape transformation of pre-grown crystals over time (e.g cubic to rhobooctahedral to octahdral and back). The authors start with seed crystals of specific morphology and then immerse the pre-grown crystals in a second solutions with additives to direct the crystal growth. This strategy allowed them to develop a general scheme to determine the relative order of surface energies and form new crystal shapes containing planes that cannot be directly stabilized by preferential adsorption alone.

Course Level:

Prerequisites:

Corequisites:

Subdiscipline:

Science Skills, Practices, and Resources

Five Slides About a Simple powder XRD Analysis

Learning Goals:

After reading and discussing this paper, students will be able to:

- Differentiate between notations describing planes, directions, and families of planes

- Describe atomic surface terminations of different crystal faces of the same unit cell

- Describe the effect of common additives on synthesis of crystals

- Determine d-spacings of planes from XRD data

- Determine lattice parameters from XRD data

Topics Covered:

Chemical literature

Diffraction

Nanoscience

Related activities:

Implementation Notes:

I used this article in the Spring of 2014 in a class of 9 (1 freshmen, 1 sophomore, 5 juniors, 2 seniors) as our conclusion of our discussion of solid state chemistry. Students had a background in electrochemistry, crystal structures and x-ray diffraction before reading this paper. Students were required to submit the first set of questions when they came to class and then they worked on the second set of questions in small groups. During the class discussion, we reviewed electrochemistry, in particular the reaction of electrodeposition of Cu²⁺ to Cu₂O and revisited Pourbaix diagrams briefly to discuss stability of different metal oxide species. We also discussed preferential adsorption and how this impacts crystal growth. For a good paper on preferential absorption, see Matthew J. Siegfried and Kyoung-Shin Choi, “Electrochemical Crystallization of Cuprous Oxide with Systematic Shape Evolution,” Adv. Mater. 2004, 16, 1743-1746. (dx.doi.org/ 10.1002/adma.200400177). Schematic 1 is particularly helpful and I used it to develop the concept preferential adsorption and the relative enrgies of planes.

Time Required:

50 minutes

Web Resources:

Elucidating the Effect of Additives on the Growth and Stability of Cu2O Surfaces via Shape Transformation of Pre-Grown Crystals

29 Jun 2015

Introduction to Miller Indices

Submitted by Vanessa McCaffrey, Albion College

Evaluation Methods:

I evaluated the students' understanding of and engagement in the material by two different methods.

First, students received a participation grade. They were were required to ask questions on at least one of the pages and answer one of the games on the "Question" page.

I evaluated their factual knowledge during literature discussions later in the semester.

There were no homework or exam questions that were specific to this material. However, this will change the next time and there will be some follow-up homework. I will post this HW assignment as a separate learning object when it is completed.

Evaluation Results:

Overall, the activity was a success. In the course evaluations at the end of the semester, students reported liking the website activities (I used several from the University of Cambridge DoITPoMS Teaching and Learning Packages throughout the semester) better than reading assignments that came from the book. They reported liking the animations and the hands-on learning.

In a later literature discussion (see related LO), students were able to answer questions about the peaks in the XRD and what the different numbers meant.

Description:

Towards the end of the semester, when we were starting to read more of the primary literature, I realized that the Miller Indices were present in most of the papers that I wanted to discuss. However, I couldn't find any good resources in textbooks that would help to explain what these were. I found this online resource through the University of Cambridge that is engaging, interactive and concise.

Corequisites:

Prerequisites:

Course Level:

Topics Covered:

Learning Goals:

The tutorial website does an amazing goal of outling the specific learning goals here.

In brief, the learning goals for student are:

Gain an understanding of Miller Indices
Given a set of numbers, generate the unit cell plane
Determine the set of Miller Indices given a plane in a unit cell
Describe how Miller Indices can be used in the "real world" through literature examples

Subdiscipline:

Tuning the band gap of CZT(S,Se) nanocrystals by anion substitution

Related activities:

Implementation Notes:

I sent the website out to the students about a week before class and asked them to read the first eight sections (through "Bracket Conventions") and also the section on "Practical Uses". I told them that we would discuss the material in class and then go through some of the Games in the "Questions" section. I intentionally left out the section that dealt with the Weiss Zone Law.

There was no formal homework assignment associated with the assignment.

During class, I pulled the website up and we went through each of the sections. Once I felt that everyone had had a chance to ask any questions on each of the pages, I then pulled up the "Questions" and we answered the drag-and-drop questions as a class.

I called on students individually and had them answer questions in front of the class (we had been doing this all semester and there were only eight students). I answered the first questions and got several of them wrong, so they felt much more comfortable making mistakes.

When doing this again, I would use the entire tutorial, and not just selected sections.

Time Required:

30 minutes

Web Resources:

Lattice Planes and Miller Indices

10 Jun 2015

Education Resources at Beloit College - Materials Chemistry, Nanoscience and Solid State Chemistry

Submitted by Barbara Reisner, James Madison University

Description:

The resources on this website will help students learn concepts in materials chemistry, solid state chemistry, and nanoscience. The website provides links to

a video lab manual,
a cineplex of demonstrations,
kits that can be used for extended structures, and
interactive structures of solid state materials, Au nanoparticles and forms of carbon.

There videos and resources have applications across the chemistry curriculum. Many materials are inorganic. This is a great resource for people looking for ways to incorporate the new CPT guideline to discuss macromolecular, supramolecular, mesoscale and nanoscale systems within the framework of their existing curriculum.

Course Level:

Subdiscipline:

Science Skills, Practices, and Resources

Bonding models: Extended systems

Topics Covered:

Diffraction

Electronic spectroscopy

Extended structure

Nanoscience

Physical properties

Thermodynamics

Prerequisites:

No Prerequisites

Corequisites:

Beloit College Educational Resources (on Materials, Solid State and Nano-chemistry)

Web Resources:

6 Jan 2015

Zeolite Synthesis

Submitted by Erica Gunn, Simmons College

Evaluation Methods:

Lab notebooks were collected and graded for all students. In addition to a condensed introduction and thorough lab procedure/observations section, students discussed how well their x-ray data matched (or didn't match) the results of the instructor and other students in the lab. (Ideally, we would have compared to an inorganic structural database, but our campus does not subscribe to these sites, and I was unable to find a free one. If this resource were available, it would be interesting to have students assign peaks and calculate cage size based on diffraction angle.) Each student wrote a short conclusion and discussion of experimental error and answered the postlab questions.

Description:

This lab was part of the materials science portion of my second-year inorganic chemistry course. Students synthesize a zeolite structure and grow a chemical garden as examples of silicate chemistry.

I paired this lab with several prelab exercises that included visualizing the zeolite structure (see related activities), reading a current literature article related to an active research collaboration at the school, and writing a step-by-step procedure from the literature methods section to gain practice in planning out experiments (and to appreciate the differences between lab manul procedures and a formal methods section). For simplicity, these prelab components have been eliminated from the VIPEr version of the lab, but the experiment could easily be expanded to include prelab activities that match your own research and departmental interests.

We saved the students' zeolites and attempted to use them as catalysts for the aquation of hexammine cobalt (III) complexes in a later lab experiment, but the analysis was complicated by students using inconsistent quantities of material and by residual base from the zeolite synthesis, which affected the pH of the later reaction. Since zeolite surfaces are expected to be catalytic, this might be an interesting avenue to explore in a more advanced class or with stricter experimental controls.

Course Level:

Prerequisites:

Topics Covered:

Subdiscipline:

Learning Goals:

Students will gain experience with silicate chemistry and will be introduced to the industrial applications of zeolites.

Powder x-ray diffraction will be used as an analytical tool for determining material structure.

Corequisites:

Zeolite structure database

Equipment needs:

See prep instructions for a full list of all chemicals and equipment required (quantities calculated for a 12-student lab, working individually).

Implementation Notes:

See instructor notes document.

Time Required:

4 hours, plus oven incubation and time to filter and run XRD (see instructor notes)

Web Resources:

Crystallography Open database

6 Jan 2015

Visualization of Zeolite Structure

Submitted by Erica Gunn, Simmons College

Evaluation Methods:

Student answers to the activity questions were collected and graded based on participation/completeness.

Evaluation Results:

Despite some technical difficulties, all students were able to access the site and seemed to find the activity helpful for understanding the zeolite cage structure. Almost all students were able to count the number of cages, identify high-symmetry orientations, and all but a few were able to draw the position of oxygen atoms in the structure successfully. Most identified the pores correctly in the expanded-view structure, though a few students had difficulty orienting the pore direction correctly relative to the unit cell dimensions.

Description:

Students use a Java-based website to explore the faujasite zeolite structure. The activity questions guide them through identifying different atomic positions within the structure, and orienting the zeolite pores and "cages" relative to the crystal axes.

Learning Goals:

Students will use computer modeling to visualize the 3D crystal structure of a zeolite, and will identify "cage" and pore structures within the solid.

Corequisites:

Subdiscipline: