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Yong-jun Gao
Weixin Song
Jingbo Louise Liu
Sajid Bashir Editors

Advances in
Sustainable
Energy
Policy, Materials and Devices
Advances in Sustainable Energy
Yong-jun Gao • Weixin Song •
Jingbo Louise Liu • Sajid Bashir
Editors

Advances in Sustainable
Energy
Policy, Materials and Devices
Editors
Yong-jun Gao Weixin Song
Hangzhou Branch of the Zhejiang Department of Materials
Tsinghua Yangtze River Delta University of Oxford
Research Institute Oxford, UK
Clean Energy and Energy Conservation
and Environmental Protection Centre Sajid Bashir
Hangzhou City, China Department of Chemistry
Texas A&M University – Kingsville
Jingbo Louise Liu Kingsville, TX, USA
Texas A&M University – Kingsville
Kingsville, TX, USA

ISBN 978-3-030-74405-2 ISBN 978-3-030-74406-9 (eBook)

https://doi.org/10.1007/978-3-030-74406-9

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland
AG 2021
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Preface

At the time of starting this book with Springer Nature, I lost my doctorate advisor
(‘academic father’), and at the start of writing for the actual monograph, I lost my
biological father from severe acute respiratory syndrome (SARS), a ribonucleic acid
encoded virus with a corona geometry. At present SARS is probably the most well-
known phrase and has affected everyone in all sectors of society. “To lose one
parent, Mr. Worthing, may be regarded as a misfortune; to lose both looks like
carelessness.”―Oscar Wilde, The Importance of Being Earnest. Like, Mr. Wilde, I
reflect on, where we are as a society.
During this reflection period, when most of us are working remotely, teleconfer-
encing, or are limited in how many people can work in any laboratory, we have to
ask is Sustainable Energy Necessary? and if yes, what is the likely energy production
roadmap over the next five decades?
This monograph aims to address this central thematic question and is split into
several themes, relating to energy generation from coal, hydrogen, thermal heat,
light, electrons, and associated storage to ensure a continuous supply of electricity as
demanded by industry, residual, home and businesses.
The authors cover themes related to the above mission and in this preface as
editors will summarize and expand the scope (1-Bashir) contained within the pages
of this monograph. The first three chapters deal with photocatalysis concerning solar
energy (2- Li/Kong), hybrid nature-derived mimetics (3-Bai/Ran), and the first
principle-based density level theory calculations (4-Tang). The next four chapters
deal with the production of hydrogen or oxygen or their utilization, with clean
hydrogen production technologies (5-Abdullah), from metal hydride (6-Corgnale)
and oxygen reduction using ruthenium electrocatalysts for direct methanol fuel cell
devices (7-Uribe-Godínez) and direct conversion of carbon dioxide to oxygenates
(8-Spivey). We return to the theme of solar energy is respect to solar thermal fluids
thermodynamics (9-Kalita), modeling (10-Fox/Bashir), and electrolysis (11-Haik).

v
vi Preface

The theme of energy storage is dealt with in the next two chapters with a focus on
transition metal-based electrochemical storage (12-Huda) and an emphasis on mixed
vanadium oxides (13-Li). We then explore an application of certain metal oxides in
the form of metal-organic frameworks for water adsorption (14-Wang), advanced
materials for supercapacitors (15-He), or metal layered two-dimensional MXenes for
electrochemical storage as a departure from traditional metal oxides, addressed
earlier in the monograph (16-Luo). The role of solid-electrolyte in high-density
lithium-ion batteries is discussed next (17-Qiao) and the modern characterization
approach to better understand energy materials is further explored as a standalone
topic for X-ray energy (18-Tan/Shearing) or advanced transmission electron
microscopy(19-Robertson). We then break the next segment to discuss clean coal
(20-Meyer), coal and biomass gasification (21-Guan), energy from lignocellulosic
materials (22-El-Azazy/Shibl), and how these materials can be used for sustainable
development. Two examples are used to illustrate this approach. The role of Munic-
ipal solid waste incineration (23-Quina) and carbon sugars as fuels for microbial fuel
cells, both theory and actual practice is extensively reviewed (24-Liu). The last
segment policy, energy materials and electrification in china in two perspectives, one
from the application of artificial intelligence in the monitoring of smart devices and
applications such as electric vehicles (25-Gao) and the application of blockchain,
smart devices and photovoltaic/wind/hydrogen stored energy in a delocalized grid as
a framework for renewables energy (26-Gao) and the monograph ends with a general
review of themes covered by one of our editors (27-Song) with the back matter
subject index.
All authors justify the role of energy storage or application of sustainable energy
to lessen the influence of carbon dioxide that is derived from the combustion of coal
to generate electricity. Fossil fuels such as coal and natural gas are the mainstay for
electricity generation both within the United States and globally as observed in
figure 1, however at the cost of reliable and relatively cheap electricity from coal is
the expense of emissions from soluble oxides of carbon, nitrogen, and sulfur, as well
as particulate matter. This has an environmental cost associated with it and will
contribute towards respiratory distress, which in turn will enhance the susceptibility
of a slice of the population towards SARS. Lastly, should carbon be used to generate
thermal heat or used to manufacture materials, drugs, plastics, paints and other useful
resources is a question that is being asked to generate a circular economy where
waste is minimized and each atom is utilized, a form of conversation of matter?.
The authors within this monograph highlight a few of the approaches that are
currently under development at the technical level of attainment. The review and
case studies are broad because the challenges are diverse, such as the development of
clean biofuels for aviation, transportation and heating and cooling, waste to energy
conversion technologies, a value-added material transformation from waste and life
cycle assessment. On the proceedings page, we as the editorial team will further
develop some areas that we consider emerging and pivotal towards the development
of strategies to engineering a future with zero carbon emissions and cheaper energy
resources that are sustainable.
Preface vii

Any project, be it a greeting card, a book chapter, a review article, or a grant

proposal is an intense endeavor and almost always a team effort; this monograph is
no different, which we acknowledge here. Charlotte Hollingworth, for the day-to-
day management, pre-print layout of the various manuscripts and Solomon, Cynthia,
and Sharon also at Springer (Springer Science+Business Media, LLC) for taking an
idea based on our work within the American Chemistry Society (ACS) division of
energy and fuels (ENFL, Liu and Bashir), and support from Texas A&M University-
Kingsville.
Lastly, we pay our respects to Peter J Derrick and Mohammed Bashir who died
recently. A short biography can be found here for Dr. Derrick at https://doi.org/
10.1177/1469066717739174. Thank you, Peter, and Dad your legacy will endure.

Kingsville, TX, USA Sajid Bashir

Kingsville, TX, USA Sai Chava

Oxford, UK Weixin Song

Hangzhou City, China Yong-jun Gao

Kingsville, TX, USA Jingbo Louise Liu

Contents

1 Promising Clean Energy Development: Practice, Challenges,

and Policy Implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Sajid Bashir, Sai Chava, Weixin Song, Yong-jun Gao,
and Jingbo Louise Liu
2 Applications and Fundamentals of Photocatalysis
with Solar Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Qiuyang Huang, Dan Kong, and Yongdan Li
3 Functional Nucleic Acid Hybrid Materials for Photovoltaic Cells:
Design, Fabrication, and Performance . . . . . . . . . . . . . . . . . . . . . . 67
Dan Bai, Huhu Feng, Xingchen Yu, Chenxin Ran, and Wei Huang
4 First-Principles Calculations for the Interfaces of Perovskite
Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Jun-Peng An, Ying Tian, Hong-Tao Xue, Jun-Chen Li,
Jun-Qiang Ren, Xue-Feng Lu, and Fu-Ling Tang
5 Clean Hydrogen Production Technologies . . . . . . . . . . . . . . . . . . . . 159
Mohammad Yusuf, Mohamad Sahban Alnarabiji,
and Bawadi Abdullah
6 Thermal Hydrogen Compression Based on Metal
Hydride Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Claudio Corgnale, Robert C. BowmanJr., and Theodore Motyka
7 Oxygen Reduction Reaction Performed by Ru-Based Catalysts . . . . 193
J. Uribe-Godínez and A. Altamirano-Gutiérrez
8 Direct Catalytic Low-Temperature Conversion of CO2
and Methane to Oxygenates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Ashraf Abedin and James J. Spivey

ix
x Contents

9 Heat Transfer Analysis in Solar Thermal Collectors . . . . . . . . . . . . 251

Pankaj Kalita, Dudul Das, Samar Das, Rabindra Kangsha Banik,
and Urbashi Bordoloi
10 Heat Transfer Fluids in Concentrating Solar Power Systems:
Principle and Practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
Elise B. Fox, Sai Raghuveer Chava, Jingbo Louise Liu,
and Sajid Bashir
11 Electrocatalysis for the Water Splitting: Recent Strategies
for Improving the Performance of Electrocatalyst . . . . . . . . . . . . . . 315
Tanveer ul Haq and Yousef Haik
12 Future of Electrochemical Energy Storage and Its Impact
on the Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Nazmul Huda and Shahjadi Hisan Farjana
13 The Application in Energy Storage and Electrocatalyst
of Vanadium (Based) Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
Yue Wang, Fan Li, Sajid Bashir, and Jingbo Louise Liu
14 Water-Stable Metal-Organic Frameworks for Water
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Xuan Wang and Charles Lee
15 Supercapacitors: History, Theory, Emerging Technologies,
and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
Yiyang Liu, Paul R. Shearing, Guanjie He, and Dan J. L. Brett
16 Interlayer Structural Engineering of 2D MXene
for Electrochemical Energy Storage . . . . . . . . . . . . . . . . . . . . . . . . 451
Jianmin Luo
17 The Role of Ex Situ Solid Electrolyte Interphase in Lithium
Metal Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
Rajesh Pathak, Yue Zhou, and Qiquan Qiao
18 3D X-Ray Characterization of Energy Storage and Conversion
Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
Chun Tan, Andrew S. Leach, Thomas M. M. Heenan, Rhodri Jervis,
Dan J. L. Brett, and Paul R. Shearing
19 In Situ Transmission Electron Microscopy for Studying
Lithium-Ion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
Chen Gong, Shengda Pu, and Alex W. Robertson
20 Clean Coal Conversion Processes–The Present and Future
Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
E. Gerald Meyer, Sai Raghuveer Chava, Jingbo Louise Liu,
and Sajid Bashir
Contents xi

21 Coal Gasification with Exergy Recuperation and CO2 Recovery . . . 593

Zhongkai Zhao, Yohanes Andre Situmorang, Atsushi Tsutsumi,
Xiaogang Hao, Abuliti Abudula, and Guoqing Guan
22 Lignin and Lignocellulosic Materials: A Glance on the Current
Opportunities for Energy and Sustainability . . . . . . . . . . . . . . . . . . 621
Marwa El-Azazy, Sajid Bashir, Jingbo Louise Liu,
and Mohamed F. Shibl
23 Municipal Solid Waste Incineration and Sustainable
Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
Beatriz Sales Bandarra and Margarida J. Quina
24 Microbial Fuel Cells: Design and Evaluation of Catalysts
and Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
Sajid Bashir, Shawn P. Mulvaney, William Houf, Luis Villanueva,
Zhaohui Wang, Gregory Buck, and Jingbo Louise Liu
25 Observation on Comprehensive Energy Trend . . . . . . . . . . . . . . . . 765
Rui Guan, Yunchuan Wang, Sai Raghuveer Chava,
Jingbo Louise Liu, Sajid Bashir, and Yong-jun Gao
26 Smart Energy Trend Observation . . . . . . . . . . . . . . . . . . . . . . . . . . 797
Ran Wei, Yong-jun Gao, Zhihua Wu, Sai Raghuveer Chava,
Jingbo Louise Liu, and Sajid Bashir
27 Postface: Conclusion on Renewable Energy Strategies
for a Sustainable Future: Part A: Role of Energy Storage . . . . . . . . 839
Weixin Song, Yong-jun Gao, Sajid Bashir, and Jingbo Louise Liu

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
About the Editors

Yong-jun Gao, a Postgraduate trained and is at present

the Deputy Director of Clean Energy and Energy Con-
servation and Environmental Protection Center, Zhe-
jiang Yangtze River Delta. Since 2001, he has been
doing research and work in the fields of energy and
environmental protection. He has won the second aca-
demic prize of China Nuclear Energy Association, the
third academic prize of China Electricity Council, and
the second prize of the science and technology manage-
ment innovation of State Power Investment Corporation
Limited. He has published many articles as the first
author or co-author in publications such as China
Nuclear Power, Nuclear Power Engineering, China
Power Enterprise Management, East China Electric
Power, and Nanostructured Materials for next-
generation Energy Storage and Conversion. He was
awarded the model worker and the May Day medal by
a Chinese city.

Weixin Song is an MPLS Enterprise Fellow and Post-

doctoral Research Fellow at the University of Oxford.
He received his Ph.D. in Material Electrochemistry from
Imperial College London in 2019 funded by the Presi-
dent’s Ph.D. Scholarship. He has been a member of the
Centre for Doctoral Training (CDT) of Advanced Char-
acterization of Materials and the London Centre for
Nanotechnology (LCN). He completed his BSc in
2012 and MSc in 2015 from Central South University,
China. He has research interests in materials electro-
chemistry and characterization with materials
xiii
xiv About the Editors

application in energy storage, electrocatalysis, and

photo electrocatalysis. He is particularly interested in
the materials and interface studies using electron
microscopy and spectroscopy. He has 22 first-author
publications and 18 licensed patents. He has contributed
chapters on one book published by Springer. He
received the highest student honor of Central South
University (2014), STFC Future Early Career Award
(2016), Armourers & Brasiers Rolls-Royce Scheme
Grant (2018), National award for outstanding self-
financed students abroad (2018), MPLS Enterprise Fel-
lowship (2019) and Constance Fligg Tipper Centenary
Memorial prize (2020).

Jingbo Louise Liu received her Ph.D. in Materials

Science and Engineering from the University of Science
and Technology Beijing (China) in 2001. She com-
pleted her postgraduate training at the University of
Calgary in Alberta (Canada) in electrochemistry analy-
sis of nanomaterials. She is at present a Full Professor at
Texas A&M University-Kingsville (TAMUK, USA)
and focused on materials preparation, characterization,
and applications. She is a Fellow of the Royal Society of
Chemistry, a Vebleo Fellow, and a Fellow of the Inter-
national Association of Advanced Materials Society.
She also holds Chartered Chemist status and separately
Chartered Scientists status from the Science Council,
UK. She also holds DEBI Faculty Fellow status at the
US Air Force Research Laboratory and is a past JSPS IF
(Japan) and FFSI in Israel awardee recipient respec-
tively. She has authored and co-authored, books, book
chapters, and peer-reviewed journal articles (> 100).
During her 12.5-year services at TAMUK, in chemistry,
she has taught > 8700 students and trained about 150 stu-
dents and scholars to conduct leading-edge research.
She directed and /or participated in the projects (> 40)
supported by the NSF (US and China), NSERC (CAN-
ADA), ACS Petroleum Research Funds, and Depart-
ment of Education as PI, Co-PI, and senior personnel.
She was recently elected as the Division Program Chair,
Chair-Elect, and Chair of Energy and Fuels of the
American Chemical Society.
About the Editors xv

Sajid Bashir received his Ph.D. training in matrix-

assisted laser desorption/ionization time-of-flight mass
spectrometry from the University of Warwick (UK) in
2001 and previously graduate training in Fourier trans-
form ion cyclotron resonance mass spectrometry from
the University of New York at Buffalo (USA). He was a
postgraduate research associate at Cornell University
(USA) in the field of plant proteomics. Currently, he is
a Full Professor at Texas A&M University-Kingsville
(TAMUK) and a past Faculty Fellow at the US Air
Force. He has directed and participated in more than
20 projects supported by the Welch Foundation,
TAMUK, Texas Workforce Commission, and US
National Institute of Health. He has co-authored >
80 book chapters and peer-reviewed journal articles.
He is a fellow of the Royal Society of Chemistry, and
also holds Chartered Chemist and separately Chartered
Scientists from the Science Council (UK). He is also the
American Chemical Society, Energy and Fuels Division
Technical Secretary (2018–2022). During his service at
TAMUK, he trained more than 3000 students on both
undergraduate and graduate levels. He created online
courses and established safety training protocols in con-
junction with Risk Management. Currently, he collabo-
rated with local law enforcement as a consultant in
forensic chemistry.
Abbreviations

δ Delta
α Elevation Angle
λ Wavelength
Φ Polarization Potential
θ Theta
Φfb Flat Band Potential
ΔT Charging/ Discharging Cycle Time
φ Latitude Of The Collector
(A)ZIB (Aqueous) Zinc Ion Batteries
abs Absorption
AC Activated Carbon
ACN Acetonitrile
AFC Alkaline Fuel Cell
AOR Alcohol Oxidation Reaction
ASU Air Separation Unit
ATR Auto-thermal Reforming of Methane
BFB Bubbling Fluidized Bed
BP Black Phosphorus
CAES Compressed Air Energy Storage
CB Conduction Band
CBM Conduction Band Minimum
CCS Carbon Capture and Storage
CCS CO2 Capture and Storage
CCT Clean Coal Technology
CE Coulombic Efficiency
CFB Circulating Fluidized Bed
CFS Capacitive Faradic Storage
CH Helmholtz layer capacitance
CHP Combined Heat, and Power
CLG Chemical Looping Gasifier
CNF Carbon Nanofibers
xvii
xviii Abbreviations

CNT Carbon Nanotubes

CNT Carbon Nanotubes
CO Carbon Monoxide
CO2 Carbon Dioxide
COF Covalent Organic Frameworks
COS Carbonyl Sulfide
CP Conductive Polymers
CQD Carbon Quantum Dots
CRM Critical Raw Materials
CS2 Carbon Disulfide
CSC Charge layer capacitance
CSC China Scholarship Council
CSP Concentrated Solar Power
CT Computed Tomography
CTMA Cetyltrimethylammonium Chloride
CV Cyclic Voltammetry
CVD Chemical Vapor Deposition
DBCFB Dual-Bed Circulating Fluidized Bed
DEPG Dimethyl Ether of Polyethylene Glycol
des Desorption
DFT Density Functional Theory
dI Decrement of the Light Intensity
DL Double Layer
DMC Dimethyl Carbonate
DMF N, N-Dimethylacetamide
DMFC Direct Methanol Fuel Cell
DOS Density Of States
dx Film Thickness
E Occupied by the electrons
Ec CB Energy
EC Ethylene Carbonate
EDC Ethylene Dicarbonate
EDLC Electric Double-Layer Capacitors
EF Fermi Level
EMC Enterprise Management Console
EPRI Electric Power Research Institute
ESPW Electrochemical Stable Potential Window
ESR Equivalent Series Resistance
ETC Evacuated tube collectors
EU European Union
EUV Extreme Ultraviolet
Ev VB Energy
FEC Fluoroethylene Carbonate
FOM Figure Of Merit
Abbreviations xix

FPC Flat Plate Collectors

FST Foundation for Science and Technology
GBL γ-ButyroLactone
G-C-S Gouy-Chapman-Stern
GHG Greenhouse Gases
GO Graphene Oxides
GPL Gel Polymer Electrolyte
GTE Gross Thermal Efficiencies
H 2O Water
H 2S Hydrogen Sulfide
HCN Hydrogen Cyanide
HDFC Housing Development Finance Corporation
HER Hydrogen Evolution Reaction
HF Heating Fluid
HHV Higher Heating Value
HOMO Highest Occupied Molecular Orbital
HOR Hydrogen Oxidation Reaction
HRSG Heat Recovery Steam Generator
HTFT High-Temperature Fischer-Tropsch Synthesis
HTMM High-Temperature Mixing Method
HyPr-RING Hydrogen Production by Reaction-Integrated Novel Gasification
hν Photon Energy
I Light Intensity
IBA Bottom Ash
ICT Information and Communications Technology
IEA International Energy Agency
IFA Fly Ash
IGCC Integrated Coal Gasification Combined Cycle
IGFC Integrated Coal Gasification Fuel Cell
IHP Inner Helmholtz Plane
IoT Internet of Things
IRENA International Renewable Energy Agency
ISE Inorganic Solid Electrolytes
k Boltzmann Constant
KIB Potassium Ion Batteries
KPI Key Performance Indicators
LAB Lead-Acid Batteries
LCI Life Cycle Impact
LDH Layered Double Hydroxides
LIB Lithium-Ion Batteries
LMA Lithium Metal Anode
LMB Lithium Metal Batteries
LSV Linear Sweep Voltammetry
LUMO Lowest Unoccupied Molecular Orbital
xx Abbreviations

MCFC Molten Carbonate Fuel Cell

MEA Membrane-Electrode Assemblies
MeOH Methanol
METI Ministry of Economy, Trade, and Industry
MEXT Ministry of Education, Culture, Sport, Science, and Technology of
Japan
MH Metal Hydride
MIEC Mixed Ionic/electronic Conductors
MO Methyl Orange
MOF Metal-Organic Frameworks
MSW Municipal Solid Waste
Nc Effective Densities of CB
NEA National Energy Administration
NFCS Non-Faradaic Capacitive Storage
NMP N-Methyl-2-Pyrrolidone
Nv Effective Densities of VB
OER Oxygen Evolution Reaction
OHP Outer Helmholtz Plane
OOH Adsorbed (per) Hydroxide species
OOR Oxidation of Organic Reactant
ORR Oxygen Reduction Reaction
PAFC Phosphoric Acid Fuel Cell
PAH Polycyclic Aromatic Hydrocarbons
PANI Porous Nano flower Polyaniline Electrode
PC Propylene Carbonate
PC Propylene Carbonate
PCB Polychlorinated Biphenyls
PCBM Phenyl-C61-Butyric Acid Methyl Ester
PCDD Polychlorinated Dibenzo-p-Dioxins
PCDF Polychlorinated Dibenzofurans
PCE Power Conversion Efficiency
PCM Phase Change Material
PCP Porous Coordination Polymers
PDDA Poly Diallyl Dimethylammonium Chloride
PEC Photoelectrochemical
PEMFC Proton Exchange Membrane Fuel Cell
PHES Pumped Hydro Energy Storage
PM Particulate Matter
PPy Polypyrrole
PSC Perovskite Solar Cells
PTFE Ethylene Polytetrafluoride
PVA Polyvinyl Alcohol
QFL Quasi-Fermi Level
RDE Rotating Disk Electrode
Abbreviations xxi

RDS Rate-Determining Step

ROS Reactive Oxygen Species
SARS Severe Acute Respiratory Syndrome
SC Supercapacitors
SDC Static Dielectric Constant
SEI Solid Electrolyte Interphase
SGSP Salt Gradient Solar Pond
SHE Standard Hydrogen Electrode
SIB Sodium-Ion Batteries
SNCR Selective Noncatalytic Reduction
SOFC Solid Oxide Fuel Cell
SOHIO Standard Oil of Ohio
SPE Solid Polymer Electrolyte
SRM Steam Reforming of Methane
SSE Solid State Electrolyte
STEM Scanning Transmission Electron Microscopy
STP Standard Temperature and Pressure
TBCFB Triple-Bed Combined Circulating Fluidized Bed
TES Total Energy Supply
TFE TetraFluoroethylene Copolymer
TGA Thermo Gravimetric Analysis
TiO2 Titanium Dioxide
TMB Transition-Metal Based
TMO Transition Metal Oxides
TOC Total Organic Carbon
TXM Transmission X-ray Microscopy
UPD Under-Potential Deposition
VB Valence Band
VBM Valence Band Minimum
VOC Volatile Organic Compounds
Chapter 1
Promising Clean Energy Development:
Practice, Challenges, and Policy
Implications

Sajid Bashir, Sai Chava, Weixin Song, Yong-jun Gao, and Jingbo Louise Liu

Dedicated to Dr. Peter J Derrick and Mr. Mohammed Bashir,

Rest in Peace.

1.1 Fossil Fuels: A Prolog

To achieve this conversation of mass principle where atoms are converted from one
form to another, waste heat and energy should be recaptured and retasked, and
converted to value-added materials. As is known in freshmen chemistry, one mole of
carbon generates one mole of carbon dioxide, using methane as an example. Coal

S. Bashir (*)
Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA
e-mail: br9@tamuk.edu
S. Chava
Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA
Emergent Biosolutions, San Diego, CA, USA
e-mail: sairaghuveer@gmail.com
W. Song
Department of Materials, University of Oxford, Oxford, UK
e-mail: weixin.song@materials.ox.ac.uk
Y.-j. Gao
Center for Clean Energy and Energy Conservation and Environmental Protection, Zhejiang
Yangtze River Delta, Hangzhou, People’s Republic of China
Sunshine Times Law Firm, Hangzhou, People’s Republic of China
e-mail: gggycpp@sina.com
J. L. Liu
Department of Chemistry, Texas A&M University-Kingsville, Kingsville, TX, USA
Texas A&M Energy Institute, College Station, TX, USA
e-mail: kfjll00@tamuk.edu; jingbo.liu@tamu.edu

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2021 1

Y.-j. Gao et al. (eds.), Advances in Sustainable Energy,
https://doi.org/10.1007/978-3-030-74406-9_1
2 S. Bashir et al.

being a multimeric component generates multiple moles of carbon dioxide, as well

as nitric oxides and oxides of sulfur:

4 C85 H5 O7 N2 S2 þ 351 O2 ! 340 CO2 þ 8 NO2 þ 8 SO3 þ 10 H2 O

Combustion of bituminous coal will generate approximately 85 moles of CO2 per

mole of coal or 24 megajoules per kilogram or 1000 g of CO2eq for each kWh
generated, while natural gas is approximately at 500 g CO2eq per kWh. Therefore,
technologies that improved combined heat and power such as recapture heat from
waste incineration will result in lower consumption of coal and natural gas. In
general, the electricity demand has increased annually globally by 3% although,
with the more advanced infrastructure of the United States, the increase is less, there
is an increased demand in energy generation from a mix of resources, principally
coal and Natural gas, followed by hydro and nuclear [1].
Since 2010, there has been a renewed emphasis on a transition to renewable
energy (Fig. 1.1), where the first transition was going from wood/peat moss locally
to coal enabling the early societies to become more mobile. In the modern
preindustrial era, coal becomes the engine for change, which enables the Romans,
Greeks, and Chinese to use coal for heat and forging of weapons. The British
industrial revolution was powered by coal to provide heat for steam engines,
buildings, and generate electricity and manufacture steel. The second transition is
in the early 1970s as the economy transitioned to more natural Gas due to the Oil

Fig. 1.1 Summary of energy generation by nuclear, petroleum distillates, and renewable resources
(left-axis) and fossil fuels (Coal, and Natural Gas, right axis; [2–6])
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 3

Crisis and to lower carbon dioxide emissions. We are in the third type of transition to
a more sustainable form of generating energy [7].
A levelized cost of electricity from different energy resources by the Institute of
Energy Research suggests that retrofit of current coal and gas power plants to extend
their useless operating lifespans by 15 years could yield near-zero carbon dioxide
emissions as the most reliable and cheapest form of energy production. Under such a
scenario, soluble oxide of carbon, nitrogen, and sulfur are captured and carbon
dioxide is stored in geological sites suited for long-term storage [8]. The current
general-purpose analyses reported in the literature fail to connect the levelized cost
of energy to the reduction of particulate matter, solid oxides of carbon, nitrogen, and
sulfur, and second the cost to implement these technologies and their lifecycle
energy and emission [9]. This we believe is necessary before the first step before
an environmental roadmap can be fully developed and deployed [10] (Fig. 1.2).
In the area of energy capture and recycling, that waste to biofuels will take an
increasing role in the next 50 years as a necessary aid to transition away from the
utilization of coal for the generation of electricity. There are two broad reasons: One,
these resources currently exist, do not need to be mined or extracted but are
generated as a result of industrial, agricultural, and process chemistries, and are
essential ‘lost’ to the economy. If these resources can be integrated, waste is
minimized, and the extracted energy can be applied to the grid [13]. Second, the
‘lost energy’ is currently ‘replaced’ by coal and natural gas and this will enable lesser
dependence on coal. Examples of atom-conversion are the generation of biofuels

Fig. 1.2 Summary of emissions of common volatiles and particulate matter (left axis) and the price
of natural gas and coal on a megawatt-hour basis (right axis; [11, 12])
4 S. Bashir et al.

from nonfood feedstocks, such as nonedible seed oil, wood chips, grape marc,
chicken/cow manure, fruit peel, rotten plant matter, or recycling of municipal solid
waste by a thermal process, followed by aerobic respiration, fractionation using a
biorefinery process to generate bioethanol and char. These could be supported using
clay-based heterogeneous catalysis and a porous metal–organic framework to cap-
ture and store biogas [14–15].
Where the carbon source is lignocellulose biomass, the typical pretreatment is
acid wash and digestion; alkaline hydrogen peroxide application may also achieve
similar goals with lower energy balance and lesser useless by-products. Under such a
scenario, lignocellulose biomass is pretreated with hydrogen peroxide [16]. As
hydrogen peroxide has a greater oxidative potential than sulfuric acid, longer
incubation periods may yield phenomenologically similar results in terms of
delignation followed by hydrolysis described by Eq. 1.1:

E : H2 O2 þ 2Hþ þ 2e ! 2H2 O, E ¼ 1:78 V vs:S2 O8 2 þ 2e

! 2SO4 2 , E : 2:01 V ð1:1Þ

The waste can also be heated after pretreatment or subjected to co-digestion

through controlled pyrolysis to generate biochar. As biochar exhibits a high carbon
content, its caloric values are like coal and could be used for heat and power
generation or converted to use materials such as activated carbon or porous storage
materials.
In the area of biofuels, lignocellulosic organics from olive trees or organic manure
could be treated with solid weak acids using heterogeneous catalysts and powered by
concentrated solar power to generate biofuels, or if anaerobic respiration is used to
generate lactic acid as a precursor for the synthesis of poly-lactic acid polymers from
waste by-products, adding value back to the supply chain [17]. Like solid waste,
wastewater treatment is a high-energy process particularly when secondary sludge is
formed, the degree of microbial activity is still high. Wastewater microbial-rich
sludge could be subjected to anaerobic respiration and converted to inorganic salts
consisting of soluble oxides of nitrogen and phosphorus, which could be used as
renewable fertilizers, the organic digestates as biogas.

1.1.1 Life-Cycle Assessment: Common Approaches

The life-cycle assessment should account for environmental, economic, and techni-
cal parameters in the application of any energy production platform, summarized in
Fig. 1.3.
Examples of environmental parameters include generation of global warming
potential, acid rain and acidification potential, eutrophication potential, and cumu-
lative energy demand. In the area of economy, the unit cost per megawatt-hour,
operational life-cycle, infrastructure costs, and power plant operational costs
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 5

Fig. 1.3 Block diagram

summary of factors that
underpin life-cycle
assessment cradle-to-grave
type of analysis for energy
generation (fossil fuels) and
energy storage (sustainable
energy resources, [18])

including the cost of decommissioning and the technical parameters are the cost of
feedstocks, generating capacity, generating reliability, technological maturity of the
proposed process, and transmission and storage potential. An example of the above
approach is when an analysis of electrical storage is conducted on the ‘short-term’ (<
1 min), ‘medium-term’ (~ 270 min), or ‘long-term’ (> 130,000 min). By using the
general equation to determine the levelized cost of electricity as described by
Eqs. 1.2 and 1.3:

ðCapC þ OpC  AFÞ

ð1:2Þ
AF  W

where

1  ð1 þ itsÞ1
AF ¼ , ð1:3Þ
its

where capital expenditures (CapC, $), operational expenditures (OpC, $) including

the balance of plant cost, W is the annualized energy output from the storage system
(kWh). The energy output is dependent upon the number of cycles (n)  discharge
power (kW) and discharge per cycle time (ms), AF ¼ annuity factor (for l at fixed
5%), its ¼ is the cost of in-state discounts or tariffs, or subsidies ($) and l is the
lifetime of the storage system (years) in increments of 1kWh and 8-216 GWh used
from storage systems.
The cycles for storage depend on a short–medium or long time scale, with
40 (thermal or isothermal energy storage) or 100 (adiabatic energy storage) cycles
6 S. Bashir et al.

Fig. 1.4A Summary of energy storage by the form of storage (Mechanical, electrical, chemical, or
thermal in nature, [20])

Performance Costs at 100 MW

3.5

3
Pump Hydro Medium-term Storage
2.5 Compressed Air Energy Medium-term Storage
LCOE (LOG Skwh)

Pump Hydro long-term Storage

2
Battery Medium-term Storage
1.5 H2/CH4 to Power Long-term Storage
H2/CH4 to Power Medium-term Storage
1
Battery Short-term Storage
0.5 Compressed Air Energy Short-term Storage
Pump Hydro Short-term
0
H2/CH4 to Power Short-term Storage
0 50 100 150 200 250 300 350 400 450 500
–0.5
CO2 Emissions (g CO2e kWh)

Fig. 1.4B Summary of LCOE for different systems for fast, medium, and long-term energy
retrieval on a log basis with area based on modal value. (Data from Table 3.4 of [11, 19])

per day for 1 year and cost factors from [19] (Data from Table 3.4 of [19 and
Appendices of 11]) and results summarized in Fig. 1.4A by energy type, Fig. 1.4B
by LCOE and Table 1.1 [51].
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 7

Table 1.1 Summary of different storage systems in terms of power, specific energy, efficiency,
discharge capacity, the response time (fast is seconds to minutes), lifetimes (years or discharge
cycles), stability in self-discharge tendency, storage costs, power conversion system (PCS) cost, and
balance of plant (BOP) associated costs [21]
Specific
Power energy Efficiency Discharge at Response
Storage technology (MW) (Wh/kg) (%) capacity (h) time
Pumped hydro storage 100–5000 0.5–1.5 65–80 1–24 Fast
Conventional com- 5–3000 30–60 41–75 1–24 Fast
pressed air energy
storage
Lead acetate (nickel 0–40 30–50 (45– 70–80 (60– 1–5 ¼ cycle
cadmium, if different) 80) 80) (6–8)
Lithium ion 0.015–50 75–200 65–88 0.017–2 ¼ cycle
Hydrogen 0–50 400–1000 35–42 12 ¼ cycle
Thermal 50–250 80–200 14–18 1–24 Fast
Storage technology Lifetime Self-dis- Storage PCS ($/kW) BOP cost
(cycles, k) charge/day cost ($/kW)
(%) ($/kWh)
Pumped hydro storage 15 k Low 5–136 403–4644 3–30
Conventional com- 10 k Low 2–141 432–1674 3–30
pressed air energy
storage
Lead acetate (nickel 0.25–1.5 0.1–5 132–915 211–648 46–140
cadmium, if different) (1.5–3.0) (0.2–0.3) (609– (281–355) (76–130)
1210)
Lithium-ion 0.6–1.2 1–5 282–4104 161–4320 0–130
Hydrogen 0.1–1.0 Low 2–15 540–4809 11–43
Thermal 5– 0.05–1 0.059– 1–50 (kJ/kg/ 59–101
15 years 0.101 K)
Sources: For Pumped Hydro and Compressed Air Storage: [19, 20, 22–24]. For lead acetate storage:
[25–29]. For lithium-ion storage: [24, 26, 27, 28, 30, 31, 32]. For hydrogen Storage: [20, 22, 24, 26,
33–35]. For thermal Storage: [24, 36–38]. For levelized costs of electricity and lifetime cost
analysis: [22, 29, 39–50, 122]

The analysis using the LCOE equation demonstrates that Li-ion batteries and
advanced adiabatic and isothermal compressed air energy storage as suitable energy
storage platforms with low levelized costs and high reliability, whereas under a
medium time scale, pumped hydro and advanced adiabatic compressed air or energy
storage or thermal storage using molten salts or mineral oil and long-term power to
gas to power or pumped hydro, where hydrogen or methane is used to generate
electricity. The electricity would be generated using a combined cycle power plant or
proton exchange membrane fuel cells [52, 53].
8 S. Bashir et al.

1.1.2 Role of Energy Storage

Energy storage is required to enable constant power load and is driven by pumped
hydro as the historically largest share form of energy storage, with lithium-ion
batteries being a recent addition due to the rise of both solar and wind power. No
lifetime assessment cycle reviewed encompasses all the required parameters, how-
ever, parameters that drive cost and applicability are a lifetime of storage technology,
the efficiency of energy retrieval, and cycle length and depend on end-usage, with
lithium-ion batteries gaining a significant share in all stationary applications due to
greater research and development as a result of increased uptake of solar and wind as
sustainable energy resources. For long-term storage and high-need applications,
pumped hydro, compressed air, hydrogen and thermal energy storage are likely to
increase due to stricter emissions standards for automobiles, fuel cells driven trans-
port is now feasible, utilizing zeolite-based heterogeneous catalysts, for example,
bismuth vanadate as an intermediate bandgap photocatalyst that could be coupled
solar to photocatalysis through recombination of photoinduced electrons and holes
to generate hydrogen from water or coal [54, 55].

1.2 The Electron Economy

While the last two decades have seen a dramatic rise in solar and wind energy
generation resources, the future most likely will look toward a hybrid system where
energy storage will play an increasingly prominent role coupled with clean coal and
carbon dioxide capture. Figure 1.5 shows a conceptual workflow of how this could
be accomplished.
The energy generation resource such as a photovoltaic array, wind-powered
turbine, solar concentrator to steam to turbine, or hydrogen feed gas will need to
generate electricity, store it and then allow the system to utilize the stored energy.
This will be done using inverters, and heat pumps, and a direct current (DC) bus,

Fig. 1.5 Workflow of hybrid energy generation and storage [56]

1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 9

using a DC-to-DC converter and DC bus connection to alternating current (AC) bus
using inverters and the electricity or lead load connected to the AC bus. In this
manner, energy is drawn with surplus energy used to recharge the secondary or flow
batteries or electrolyzes to generate hydrogen from water, if the load is more than the
immediate power, then the energy from the stored batteries can be tapped or stored
hydrogen to generate electricity with the excess heat used to assist with steam
generation. Currently, approximately 2=3 of the total annualized cost is due to
components from the wind-powered turbine and the rest for batteries, inverters,
and hydrogen storage systems, and fuel cells. The fuel cell catalyst is the next
greatest expense and is likely to decrease as more research and development is
geared toward the automobile and residential energy sectors, where the likelihood of
supercapacitor, battery, flex-fuel, and fuel cells are used or some combination for
automobile and stationary applications [57–59].
The rapid development in alkali-metal-based batteries is driven by chemical and
physical characteristics of lithium and sodium and this is related to atomic radii,
electron affinity, and charge density, from which energy density and kinetics of
energy release are derived:
e.g. 6.9 atomic mass unit, amu per mole, 0.76 Å, 180.5  C, 3.0 V, 3860 mAg.g1 and
$5 k for lithium, Li vs. 23 amu, 1.06 Å, 97.7  C, 2.7 V 1160 mAg.g1 and $0.15 k
for sodium, Na.
The molar mass is in atomic mass units, cation radii in Angstroms, melting point
in degrees Celsius, voltage relative to standard hydrogen electrode in volts, the
energy density in milliampere hour per gram, and cost of carbonate salt on a ton
basis in United States dollars, thousand increments, respectively. These energy
parameters favor lithium-ion batteries, while environmental and economic factors
favor sodium ion-based batteries [60]. A bifurcated role is likely with lithium-ion
batteries being favored in automobiles where high energy density and fast kinetics
are required and sodium-ion batteries for stationary energy storage where high
density is not required, such as buildings or a configuration shown in Fig. 1.5 [61].
The near-future bottleneck to battery and fuel cell development is the electrocatalysts
and electrode architecture, which will ultimately define high gravi- and volumetric
energy densities at the solid electrolyte interphase (SEI) layer that limits spontaneous
reactions at the expense of thermodynamic instability and lower cell lifetime, which may
be accomplished through alloying, described in Eqs. 1.4 and 1.5 [62]:

E þ yAþ þ xē ! Ay M, ð1:4Þ

where A represents alkali metals Li or Na and E represent metalloids Si, Ge, Sn, Sb,
and P, respectively, or conversion [63]:

Ma Ob þ ðb:nÞA ! aM þ bAn O, ð1:5Þ

where M.O are metal oxides and A is alkali metals (Li or Na) such as Silicon-based
anodes with Li iron phosphate batteries, e.g. Li17Si4.
10 S. Bashir et al.

1.2.1 Public Policy and Discourse

The above paragraphs imply an electron-driven economy, while this is true to a

greater degree today, this is not a complete characterization of the likely environ-
ment-food-water-energy nexus in the next 50 years, because, within the United
States, much policy is driven at the federal level due to the muscular resources
available and at the time of writing this preface, president-elect Biden has 48 senate
votes most likely confirming his policies and the best-case scenario is of a clean
sweep of the State of Georgia Senate races, tying the US senate at fifty senators from
the Grand Old Party (Republican GOP) and the democratic party that as a slim
majority within the U.S house of representatives and either a 48–52, 49–51 minority
or a tie broken by the Vice-President and confirming Democratic policies on behalf
of the presidency of the United States. This political reality means major policy
initiates will require bipartisan support to be enacted into law. This means the Biden
Green initiative on the environment that pledges great reduction in carbon dioxide
emissions could be met through not an electron economy but a carbon majority and
hydrogen minority-driven economy, whereas natural gas and coal-powered genera-
tion of electricity are accomplished using plant upgrades to capture carbon dioxide
and conversion of biomass, coal and natural resources to hydrogen that is used to
generate energy and promote fuel cell-driven transport.
Here, the U.S Department of energy could utilize its public-partnership research fund to
promote companies to conduct subsidized research in fuel cells-driven transport, similar to a
model employed to assist E. Musk in his development of a sports electric vehicle in the early
zero–zero decades. There was bipartisan support to elicit more private sector funding for
technologies that have yet to reach maturity and widespread deployment but were further in
the development cycle than emerging technologies, much as like the National Institute of
Health (NIH) Model in support vaccine research in developing world countries related to the
human immunodeficiency viruses/acquired immunodeficiency syndrome and tropical dis-
eases that do not reach the profit margin for many US Pharma to invest in heavily. This NIH
initiative has also received support from prominent foundations such as the Gates Founda-
tion and could be a scenario whereby, the politics is removed from the policy.

1.2.2 The Hydrogen Economy

How could such an economy work in principle? Where would the hydrogen be
generated? Currently, hydrogen production, approximately 48% from natural gas,
30% from Naphtha and Oils, and 18% from coal [28] or biomass. When fossil fuels
are the feedstock, hydrogen production can be accomplished by hydrocarbon
reforming, pyrolysis. Reforming from hydrocarbons can be accomplished by
steam reforming, partial oxidation, and autothermal reforming. When generated
from biomass, this may be by bio photolysis, dark or photo fermentation, if thermo-
chemical, by pyrolysis, gasification, combustion or liquefaction, and from water
splitting as indicated in Fig. 1.5. Here, electrolysis, thermolysis, and photolysis
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 11

Table 1.2 Summary of the energy density of common fuels

Phase at Specific energy (MJ/ Energy Density (MJ/
Fuel STP Kg) kg)
Hydrogen Gas 141.9 119.9
Methane Gas 55.5 50.0
Ethane Gas 51.9 47.8
Butane Gas 49.5 29.7
Methanol Liquid 20 17.1
Ethanol Liquid 29.7 23.3
Gasoline (Cetane # 8– Liquid 45.4 42.6
14)
Diesel (Cetane # 51) Liquid 46.0 43.0
Coal Solid 15–27 12.0–36.5
Wood (C6H10O5)n Solid 15.0 9.0
Sugar (glucose) Solid 15.6 23.9
Sources and Notes’: Standard Temperature and Pressure. [64–68]

could be utilized. The advantages of hydrogen are in its high energy density when
compared with carbon-based fuels, as shown in Table 1.2 and workflow in Fig. 1.6.
Hydrogen production by steam reformation is nickel catalytic conversion of
hydrocarbons and steam to form hydrogen and carbon oxide through a series of
sequential steps, which result in the synthesis of gas (syngas), water-gas shift, and
methanation or gas purification. The feed is light hydrocarbons or naphtha; however,
the materials need to be carbon and hydrogen to avoid poisoning of the catalyst. If
the coal or feed contains sulfur, a desulfurization step is performed [69] at 3.5 MPa
and 900  C temperature using a 3:5 ratio of steam to carbon [70]. The heat is
recovered and the channel promotes the water gas shift reaction, where carbon
monoxide reacts with steam to produce hydrogen gas and is purified through a
pressure swing adsorption [71] at the expense of carbon dioxide emission, which
could be captured using supercritical conditions and the liquefied carbon dioxide
stored in geological reservoirs. Alternately, the carbon dioxide could be reacted with
hydrogen to generate wet methane [72]. This methane is re-fed back to the reformer
to generate additional hydrogen. The different gases could be separated using
Pd-based Inorganic membranes with high selectivity and at lower operational
temperatures (550  C) lowering the cost of hydrogen production to $2.0 kg with
Carbon dioxide capture and storage [73] described by the steam reformation, water-
gas shift reaction, or methanation described in Eqs. 1.6, 1.7 and 1.8:

Cn Hm ðgÞ þ nH2 O ðgÞ ! nCO ðgÞ þ ðn þ ½mÞH2 ðgÞ ð1:6Þ

WGS : CO ðgÞ þ H2 O ðgÞ ! CO2 ðgÞ þ H2 ðgÞ ð1:7Þ
Methanator : CO ðgÞ þ 3H2 ðgÞ ! CH4 ðgÞ þ H2 O ðlÞ ð1:8Þ

Partial oxidation is a similar method but using oxygen instead of air and occurs at
around 1315  C for the non-catalytic process using coal, oils, or methane [71]. The
 12

Fig. 1.6 Workflow process to produce hydrogen using ten (〇!〇) distinct processes. Each unique process and the pathway are indicated using a numbered
sequence. For example, hydrogen production by Steam reforming is shown by the process 〇, membrane separation by the process ❷, coal gasification by 〇,
biomass-based processes are shown by sequences 〇,〇 and〇. Thermo-photo- or electrolysis processes by sequences 〇,〇,〇, and 〇. CRA represents carbon-
rich acids, CBP Carbon By-products; Pe the electrical energy, HeTF Heat Transfer Fluids, HiTHeE High-temperature Heat Exchanger [68]
S. Bashir et al.
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 13

feed gas or materials are oxidized directly, or sulfur is removed, and oxygen is used
to partially oxidize hydrocarbons and syngas in a similar workflow to the steam
reformation for the catalytic process conducted at lower operating temperatures
summarized in Eqs. 1.9, 1.10, 1.11 and 1.12 [74]:

Catalytic Reformer : Cn Hm ðgÞ þ ½nO2 ðgÞ ! nCO ðgÞ þ ½mH2 ðgÞ ð1:9Þ
Non  catalytic : Cn Hm ðg=lÞ þ nH2 O ðg=lÞ
! nCO ðgÞ þ ðn þ ½mÞH2 ðgÞ ð1:10Þ
WGS : CO ðgÞ þ H2 O ðg=lÞ ! CO2 ðgÞ þ H2 ðgÞ ð1:11Þ
Methanator : CO ðgÞ þ 3H2 ðgÞ ! CH4 ðgÞ þ H2 O ðlÞ ð1:12Þ

Because coal has lower hydrogen to carbon ratio than methane, higher pressure
and temperature are required (6 MPa and 1315  C), generating non-reactant ash and
more water [75].
The above two processes are endothermal and require additional energy input, for
autothermal reformation; the initial oxidation is exothermal, and the thermal energy
is used to drive the endothermal steam reforming process to drive hydrogen produc-
tion. The oxidizer is steam, oxygen, or air as the inlet gas to the reformer to drive the
reformation and oxidation reactions to occur [76], summarized in Eq. 1.13:

Cn Hm ðlÞ þ ½nH2 O ðlÞ þ ¼nO2 ðgÞ ! nCO ðgÞ þ ð½n þ ½mÞH2 ðgÞ ð1:13Þ

Because part of the thermal energy is utilized, the overall energy demand is lesser
than the before processes, lowering the cost of production. Methane conversion to
hydrogen could be separated using a Pd membrane and could be accomplished at
lower temperatures than the non-catalytic reaction when the air was used, approx-
imately 900  C, that has to be tuned to the operating parameters of the inorganic
membrane, as a higher temperature may lead to membrane deformation and loss of
selectivity of hydrogen [77].
Hydrocarbon pyrolysis is the breakdown of hydrocarbons to hydrogen via a
thermocatalytic breakdown to carbon and hydrogen at the boiling point of the liquid
hydrocarbons. When heavy oil hydrocarbons are utilized, the decomposition tem-
perature is higher around 350  C to promote gasification of the hydrocarbon
followed by cracking or the methane to hydrogen gas as a form of decarbonization
at under 1000  C and 1 atm pressure. Pyrolysis is a gasification process and does not
involve a water gas shift or carbon dioxide absorption step. The hydrogen gas is
separated using Pd-Ag alloyed membrane at lower temperatures to avoid damage to
the membrane, the rate of separation is dependent upon the partial pressure of the
incoming gas, noting that the gas needs to be devoid of sulfur to avoid catalytic
poisoning [78].
Hydrogen gas can also be formed using biomass, where the cellulose lignin-based
materials can be converted to methanol, sugars that were generated from carbon
dioxide, and sunlight known as photosynthesis. The carbon biomass is then
14 S. Bashir et al.

thermochemically broken via pyrolysis to generate a gasified-rich distillate in meth-

ane and carbon monoxide that can be processed to generate hydrogen. Alternately,
the biomass can be liquified and combusted to ultimately generate hydrogen at
0.5 MPa and 530  C anaerobically to generate small neutral gases, hydrocarbons,
and char [79] described by Eqs. 1.14, 1.15, 1.16 and 1.17:

Cn Hm ðs=lÞ þ nH2 O ðlÞ ! nCO ðgÞ þ ðn þ ½mÞH2 ðgÞ ð1:14Þ

CO ðgÞ þ H2 O ðlÞ ! CO2 ðgÞ þ H2 ðgÞ ð1:15Þ

In biomass gasification, the biomass is converted into syngas using air, oxygen, or
steam at 1400  C and 32 atm:

Biomass ðs=lÞ þ Air ðgÞ ! H2 ðgÞ þ CO2 ðgÞ þ CO ðgÞ þ N2 ðgÞ

þ CH4 ðgÞ þ Cn Hm ðlÞ þ H2 O ðlÞ þ char ðsÞ ð1:16Þ

Biomass ðs=lÞ þ Steam ðg=lÞ ! H2 ðgÞ þ CO2 ðgÞ þ CO ðgÞ þ CH4 ðgÞ
þ Cn Hm ðlÞ þ H2 O ðlÞ þ char ðsÞ
þ tar ðsÞ ð1:17Þ

Photosynthesis from plants or fermentation by cyanobacteria, algae, and fungi

can also convert biomass to sugar-rich feedstocks that can be converted to carbon-
rich acids (CRA) and then to hydrogen gas using light energy or in the dark using
two electron reduction by a hydrogenase or nitrogenase. Some elect microbes can
directly convert water to hydrogen in a process known as photolysis, summarized in
Eqs. 1.18, 1.19, 1.20, 1.21 and 1.22 [80]:

2H2 O ðlÞ þ hv ! 2H2 ðgÞ þ O2 ðgÞ or ð1:18Þ

12H2 O ðlÞ þ 6CO2 ðgÞ þ hv ! C6 H12 O6 ðsÞ þ 6O2 ðgÞ and ð1:19Þ
C6 H12 O6 ðsÞ þ 12H2 O ðlÞ þ hv ! 12Hþ ðaqÞ
þ6CO2 ðgÞ or sugars or carbon rich acids ðCRAÞ
ð1:20Þ
C6 H12 O6 ðsÞ þ 2H2 O ðlÞ ! 2CH3 COOH ðCRAÞ ðlÞ þ 4H2 ðgÞ
þ 2CO2 ðgÞ ðfermentationÞ ð1:21Þ

C6 H12 O6 ðsÞ þ 2H2 O ðlÞ ! CH3 ðCH2 Þ2 COOH ðCRAÞðlÞ þ 2H2 ðgÞ
þ 2CO2 ðgÞ ðfermentationÞ ð1:22Þ

Cellulose/Starch are the common bio feed stocks and fermentation is carried out
at mild acidic conditions in the dark. When sunlight is used, nitrogenase can convert
CRA (e.g. acetic acid) into hydrogen and carbon dioxide, summarized in Eq. 1.23
[81]:
1 Promising Clean Energy Development: Practice, Challenges, and Policy. . . 15

CH3 COOH ðlÞ þ 2H2 O ðlÞ þ hv ! 4H2 ðgÞ þ 2CO2 ðgÞ ð1:23Þ

These reactions could be accomplished using a bio-reactor, where sugars are

digested by bacteria anaerobically in the dark to generate carbon-rich acids, that
could be used by photosynthetic bacteria using light and water described by
Eqs. 1.24 and 1.25 [82]:

C6 H12 O6 ðsÞ þ 2H2 O ðlÞ ! 2CH3 COOH ðlÞ þ 2CO2 ðgÞ þ 4H2 ðgÞ ð1:24Þ
2CH3 COOH ðsÞ þ 4H2 O ðlÞ þ hv ! 8H2 ðgÞ þ 4CO2 ðgÞ ð1:25Þ

Using glucose as the biomass, approximately 7 mol of hydrogen could be

generated per mol of glucose [83] under mild acidic conditions. The last method
to generate hydrogen is direct water splitting using sunlight [84] and redox of water.
As this is an endothermic reaction, energy from sunlight is used using a fuel cell/
electrolyzer design consisting of a cathode and anode and electrolyte with an
external current. Here, water is electrolytically broken to hydrogen and oxygen,
shown in Eq. 1.26 [85]:

2H2 O ðlÞ ! 2H2 ðgÞ þ O2 ðgÞ ð1:26Þ

The electrolysis can be accomplished using fuel cells such as proton exchange
membrane fuel cells, solid oxide electrolysis cells, where they generate proton
migrates across a membrane to the cathode to generate hydrogen, leaving water
and oxygen [86, 87]. In the solid oxide electrolyzer operated under alkaline condi-
tions, water is broken down to H+ and OH, with the hydroxide traveling through the
aqueous electrolyte to the anode to form oxygen [88], with the driving energy being
thermal instead of electrical in a fuel cell, with hydrogen in the steam feed and using
fuel cells described by Eqs. 1.27, 1.28, 1.29 and 1.30 [89]:
Alkaline Solid Oxygen Electrolyzer (Anode).

OH ðaqÞ ! O2 ðgÞ þ 2H2 O ðlÞ þ 4ē ð1:27Þ

2H2 O ðlÞ þ 2ē ! 2OH  ðaqÞ þ H2 ðgÞðcathodeÞ ð1:28Þ

Proton exchange membrane

2H2 O ðlÞ ! O2 ðgÞ þ 4Hþ ðaqÞ þ 4ē ðanodeÞ ð1:29Þ

þ
4H ðaqÞ þ 4ē ! 2H2 ðgÞðcathodeÞ ð1:30Þ

The efficiency and relative merits of hydrogen production summarized in

Eqs. (1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17,
1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29 and 1.30) are
summarized in Table 1.3A. The cost of solar thermal is due to the electrolyzer unit
and for solar, it is peak and off-peak costs plus the cost of the electrolyzer unit. For
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