MATE 6301: Nanomaterials (S2 2024) Project 1 Synthesis and Characterization of Metal-loaded Trimoda

Java Python School of Mechanical and Mining Engineering

MATE 6301 : Nanomaterials (S2, 2024)

Project 1: synthesis and characterization of Metal-loaded Trimodally porous carbon Materials

(Weight 20% of the total mark)

(Deadline for submission: 16:00, 29August2024through the Turnltln system)

INTRODUCTION

Hydrogen evolution reaction (HER) is an electrochemical reaction that splits  water molecule to produce hydrogen (H2) gas at the cost of current (Figure 1a). To improve the efficiency of H2 production, electrocatalysts are required to increase the  rate of HER. Electrocatalysts for HER involve expensive precious metals (e.g., platinum, palladium, ruthenium, etc.) due to their high catalytic activities. However, the high cost and low abundance of the precious metals limit the potential of achieving H2-powered sustainable society.

To increase the efficiency of precious metals, their nanoparticle forms are effectively loaded to porous carbon nanomaterials (Figure 1b). The use of metal nanoparticles and porous carbon nanomaterials offers great advantages of large specific surface area, exposed active sites, high electrical conductivity, and goodstability in the electrolyte (Figure 1c).[1-4]  To further enhance its performance, mesopores (2-50 nm in diameter) are introduced to these carbon materials to increase the surface area and ensure that underlying  active  sites  embedded in the carbon are more accessible to reactant molecules. This attempt, also known as pore engineering, improves  electrochemical wettability and accessibility of the reactant molecules by tuning different pore sizes on the materials. Further increasing the pore size to the macropore region (above 50 nm in diameter) can improve rate capability but will severely reduce surface  area,  and further reducing the pore to micropore region (below 2 nm in diameter) will restrict diffusion but will enhance the surface area.[3, 4]

 

Figure  1 .  (a) Chemical equation for  HER. (b) Schematic illustrations of metal-loaded porous carbon with metal nanoparticles serving as catalysts. (c) Schematic illustrations of classes of nanopores depending on their diameters.

Recently, metal-organic frameworks (MOFs) have been utilized to synthesize porous carbon materials via direct carbonization. ZIF-8, which is a type of MOF nanoparticle can be easily converted into carbon via pyrolysis (heating to high temperature) due to its abundant organic linkers in the structure (Figure 2a). The resultant carbon was able to maintain its original morphology, its rich micropores, and its high surface area.

Through  pore engineerin,  ZIF-8  nanoparticles  will  acquire  tuned  pore  distribution ranging from  micropore to  mesopore, and subsequent direct-carbonization will give rise to MOF-derived porous carbons largely inheriting the morphology and nanopores from  its  MOF  precursor.  MOF-derived porous  carbons  with  tuned  nanopores  can ensure the effective use of surface area and easy access to catalysts  (Figure  2a). Scanning electron microscope (SEM) images of the exemplary MOF, pore-engineered MOF and its porous carbon demonstrate the evolution of morphological and pore size changes at each stage (Figure 2b-e).[5]

 

Figure  2 ●  (a) Schematic  illustration  of the  synthesis  of  MOF-derived  porous  carbon derived from pore-engineered MOF. SEM images of (b) MOF, (c) pore-engineered MOF, and (d, e) MOF-derived porous carbon. Adopted from Ref. 5 with permission.

As general carbon materials do not exhibit superior HER performance due to the lack of active sites, loading metal nanoparticles can tremendously increase its electrocatalytic activity.  Unlike  pure  metal  catalysts,  metal  nanoparticles  can  be  homogeneously dispersed throughout the porous carbon surface, hence increasing its exposed active site as more reactants are accessible to metal atom.

In this project students will reveal the type ofmetal loaded to porous carbon using the  characterisation  techniques  covered  in   the  lecture●  They  will  gain  deeper understanding  on X-ray diffraction  (XRD), scanning  electron  microscopy  (SEM),  and transmission electron microscopy (TEM) as they use the knowledge from the lecture and relevant data acquired. The four materials to be studied in this project are: ZF-8, pore-engineeredzIF-8, porous carbon andmetal-loadedporous carbo.

PROCEDURES OF THE ACTIVITIES

This   project   consists   of   1   video   (synthesis)   and   3   practical   (XRD,   SEM,   TEM) demonstration sessions. Students will be given experimental procedures and data, and each student is required to write an independent report in a research-article format.

Demonstration 1 - synthesis ofmetal-loaded trimodallyporous carbon (TPC) (video demo uploaded in Blackboard)

The detailed synthesis and characterisationsofTPC can be also found in Ref. 3 and 4.

Demonstration2 - XRD Characterization ofzIF-8,  TPC, metal-loaded TPC

(08:00 - 12:00, 31 st July 2024, Location: CMM at chemistry Building (68-206)/video demo)

XRD was  introduced  in the  lecture  as  a  unique characterization tool for  elucidating crystal structure of the materials. In this demonstration, X-ray diffraction spectroscopy will be used to study the change in crystalline phases of ZIF-8, pore-engineered ZIF-8, porous carbon and metal-loaded porous carbon, and ideally identify the type of loaded metal. After  collecting XRD  data,  students  must  analyse  it to  identify the  different phases  of the  doped  metal. All students should  utilize this  data to  infer the  phase structural properties of doped metal and carbon materials.

Demonstration 3 - SEM&EDxcharacterizations ofzIF-8,  TPC, metal-loaded TPC

(8:00 -  12:009 7th August 2024, Location: CMM at Hawken Building (50- 102)/video demo)

As discussed in the lecture, SEM is a powerful imaging technique to study the surface topography  using secondary electrons  emitted  by the  materials  revealing  important surface   information    such   as    pore   size,    framework   thickness,    and   the    pore distribution/uniformity  throughout  the  surface.  And  EDX  is  an  analytical  technique often coupled with SEM that provides qualitative and quantitative data on the content of elements in the sample by detecting characteristic X-rays.

The carbon material was mounted on an aluminium stub, using conductive carbon tape to   perform.   the   SEM   analysis.   From   this,   students   will   get   a   comprehensive understanding of sample preparation, sample loading, analysis through SEM, and data curation. Additionally, the obtained data helps to understand the use of micelles for the formation of mesopore structures at the nanoscale and the EDX data provides insight into the distribution and type of loaded metal.

Demonstration 4 - TEM&EDxcharacterization ofzIF-8  TPC metal-loaded TPC

(8:00 - 12:00, 21st August2024, Location: CMM atAIBN (75 - 102)/video demo)

TEM  allows  visualizing  the  internal  structure  of  the  materials  at  the  nanoscale  in transmittance  mode,  observing  the   porous  dimension.  TEM   employs  a   beam  of electrons transmitted through a thin sample to produce high-resolution images. Proper sample preparation is crucial to obtain high-quality TEM images and accurate structural information.

From this, students will  get  a  comprehensive  understanding  of sample  preparation, sample loading, analysis through TEM and data curation. Also, TEM assists students in understanding morphology at the lattice/atomic level.

ASSESSMENT

In this project, students are required to write a project report in the following format:  (1) Title and Table ofcontents, (2) Introduction, (3) Procedure and principles, (4) Results and discusion, (5) Conclusion, and (6) References.

The following table lists the detailed marking criteria.

Item	Assess	ng cr	ter	MATE 6301: Nanomaterials (S2, 2024) Project 1 Synthesis and Characterization of Metal-loaded Trimodally Porous Carbon MaterialsR a	we	ght	ng
Introduction	Clearly illustrate the challenge and objective of the project. Logically and concisely review the background.				4
Procedure and Principles	Briefly outline the experimental procedure of the project in a logical manner Briefly present the key principles of techniques used in this project. Given insufficient but not excess detail				4
Result and discussion	Scientifically present the experimental results Comprehensively interpret and critically analyse the experimental results, from which draw experimental findings				8
Conclusion	Briefly summarize the most important findings of this study and find out the future direction				2
Writing and  presentation	Logic, structure, physical layout, and appropriate attention to detail. The work is presented in an accurate, concise, and coherent fashion. Scientific and technical style. No spelling mistakes or grammar errors. Appropriate referencing to a correctly formatted bibliography.				2

Lab report format

1 ● Introduction (400 - 500 words) ●

The lab report begins with an introduction or background about the experiment, which contains  significance  and  theoretical  relevance  to  the  experiment  with  appropriate references, advantages of hard and soft template methods, the factors affecting the synthesis,  and  different  areas  of  applications.  Finally,  conclude with the  motivation behind the study and explore novel applications for mesoporous materials.

2 ● operating principle and components (400- 500 words9 passive form) ●

The operating principle (with a suitable diagram), major components, and parameters to be controlled for accurate data acquisition will be explained in this section.

3 ● Experimental (200-400 words, passive form) ●

This section should contain an overview of the equipment, apparatus, steps involved in sample preparation and other chemicals used in the experiment. If using any specific amounts of materials, make sure the amount and its units are to be specified.

e.g.,    Poly(ethylene  glycol)-block-poly(propylene  glycol)-block-poly(ethylene  glycol) diacrylate (F127) 5g, 100 mg of ZIF-8 in 2 mL distilled water and ethanol mixture, etc.

4● Results and discussion ●

This section involves the detailed analysis of the experimental results and discusses of the   acquired   data   in   each   figure   (1   to   4)   are   explained   based   on   students understanding. Analyse the  experiment/characterization's  strengths  and weaknesses and compare them with relevant literature.

When writing a discussion, try to answer these questions:

.   What is the need for the use of MOF or metal-loaded mesoporous carbon?

.   What is the need for a particular characterization? .   What do the results indicate?

.   What is the significance of the results? .   Are there any gaps in knowledge?

.   Are there any new questions that have been raised?

NOTE: Below example data are extracted from  karappannan  et al● , Energy Environ● sci●,  2019 , 12 ,  2820- 2829 ● [6]  The   actual  data  to  be  presented  and  discussed  by students in their lab report are separate from these examples●

Peak Position	(h k l)	d-spacing (Å)
39.7	(111)	2.3
46.2	(200)	2.0
67.5	(220)	1 .4

Figure 1: (a) XRD data and (b) d-spacing obtained from individual peaks from varying (h kl) values. Adopted from Ref. 6 with permission.

 

Figure  2:  FE-SEM  images  of  (a-b)  bare  carbon  nanofiber,  (c-e)  carbon  nanofibers loaded with  Pt at different magnifications. Adopted from Ref. 6 with permission.

Figure 3: (a-d) TEM images at different magnifications and (e-h) EDX images of carbon nanofibers loaded with Pt. Adopted from Ref. 6 with permission.

In  the  result  and  discussion  section,  students  need  to  explain  carefully  the  data obtained through XRD, its peak position and d-spacing value with a short explanation about it with appropriate  references. The data obtained from  FE-SEM, the students have  to  infer  the  morphology  as  an  effect  of  the  use  of  micelle  and  its  chemical composition extracted through EDX analysis. Finally, a short description of the sample morphology and size is to be explained from the TEM images.

4● conclusion ●

The conclusion is a summation of the experiment. It should clearly and concisely state what was  learned  and  its  importance. And further  include the future  aspect  of the study.

5 . References●

Relevant references are cited in the correct format in the text, and the reference list is to be included.

SUBMISSION

This laboratory report needs to be submitted before 16:00 on the 29th August 2024 through the Turnitin system  in the Blackboard. No late submission wi be allowe. Students are encouraged to check the report using the Turn-it-inprogram or iThe nticate (access  by UQ library)  to  identify the similarity  between your  reports with  existing documents. Please be advised that students can upload the report as many times as possible for minimizing the similarity (once every day). Again9 any plagiarism will  be

heavily penalized ●

Note:  A/Professor  Shahriar   Hossain  ([email protected])  is  responsible  to  this Project, so that please send any enquiry to Professor Hossain directly when needed