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Green Energy and Technology
Samira Bagheri
Nurhidayatullaili Muhd Julkapli
Nanocatalysts
in Environmental
Applications
More information about this series at http://www.springer.com/series/8059
Samira Bagheri Nurhidayatullaili Muhd Julkapli
•
Nanocatalysts
in Environmental
Applications
123
Samira Bagheri Nurhidayatullaili Muhd Julkapli
Nanotechnology and Catalysis Nanotechnology and Catalysis
Research Centre Research Centre
University of Malaya University of Malaya
Kuala Lumpur Kuala Lumpur
Malaysia Malaysia
ISSN 1865-3529 ISSN 1865-3537 (electronic)

ISBN 978-3-319-69556-3 ISBN 978-3-319-69557-0 (eBook)
https://doi.org/10.1007/978-3-319-69557-0
Library of Congress Control Number: 2017962975
© Springer International Publishing AG, part of Springer Nature 2018

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Preface
The field of nanocatalysis has undergone an explosive growth during the past
decade, both in homogeneous and heterogeneous catalyses. Nanoparticles have a
large surface-to-volume ratio compared to bulk materials, and they are attractive to
use as catalysts. Catalysts daily accelerate and boost thousands of different chemical
reactions and thereby form the basis for the multibillion-dollar chemical industry
worldwide and indispensable environmental protective technologies. Research in
nanotechnology and nanoscience is expected to have a great impact on the devel-
opment of new catalysts. Current demand for clean and renewable energy and
environmental concerns urges researchers to approach for greener advanced oxi-
dation processes such as photocatalysis. Visible-light-driven photocatalytic water
splitting for the generation of clean hydrogen fuel and pollutant degradation for
cleaner environment are promising topics. Design and development of advanced
materials as photocatalyst is very crucial, and the success of the process lies with
materials. In this book, we have highlighted principles and mechanism of several
photocatalytic systems and design of advanced materials for their applications in
photocatalysis. Very few books are available on catalysis in production schemes or
its primary applications, such as environmental applications. This book fills that gap
with detailed discussions of enhanced photocatalytic activity by using modification
activated carbon in Chap. 1, surface modification of titania/gold nanoparticles for
photocatalytic applications in Chap. 2, black titania for photodecomposition of
organic compounds in Chap. 3, applications of titania as a heterogeneous catalyst for
degradation of landfill leachates in Chap. 4, easy separation of magnetic photocat-
alyst from aqueous pollutants in Chap. 5, solar-driven, highly stable photocatalyst
system for mitigation of organic pollutants via mixed phase titania in Chap. 6, and
layered catalyst compositions for photo-treating of industrial effluents in Chap. 7.
Kuala Lumpur, Malaysia Samira Bagheri

Nurhidayatullaili Muhd Julkapli
v
Contents
1 Enhanced Photocatalytic Activity by Using Modification

Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 1
1.1 Introduction: Basic Principles of Heterogeneous Photocatalysis
System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Activated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1 Characterization of Carbon Nanomaterials . . . . . . . . . . . . . 2
1.2.2 Transformation of Biomass to Carbon . . . . . . . . . . . . . . . . 2
1.2.3 Catalytic Transformation of Biomass to Carbon . . . . . . . . . 3
1.3 Photocatalytic Systems with Activated Carbon . . . . . . . . . . . . . . . 8
1.3.1 Effect of Surface Properties . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.2 Activated Carbon/Transition Metal Oxide
Photocatalysis System . . . . . . . . . . . . . . . . . . . . . . . . ... 11
1.4 Activated Carbon Photocatalytic Systems: Future Trend . . . . . ... 17
1.4.1 Granular and Spherical Activated Carbon
Photocatalytic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4.2 ACF Photocatalysis System . . . . . . . . . . . . . . . . . . . . . . . 18
1.4.3 Graphene/Titania Photocatalysis System . . . . . . . . . . . . . . 18
1.4.4 Titania/CNT Photocatalysis System . . . . . . . . . . . . . . . . . . 18
1.4.5 Titania: Activated Carbon Semiconductor Doped
1.4.6 Titania: Activated Carbon Nonmetal Doped
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 20
2 Surface Modification of Titania/Gold Nanoparticles for
Photocatalytic Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1 Introduction: Material Design in Photocatalysis System . . . . . . . . 25
2.1.1 Heterogeneous Photocatalysis System: Challenging
Aspect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
vii
viii Contents
2.2 Alteration on Structured of Photocatalysis System . . . . . . . . . . . . 26

2.2.1 Composites System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.2 Surface Attachment System . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.3 Doping System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3 Nanosized Gold Particle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.3.1 Gold Nanoparticles: Material Development . . . . . . . . . . . . 27
2.3.2 Gold Nanoparticles: Properties . . . . . . . . . . . . . . . . . . . . . 28
2.4 Gold-Modified Semiconductor Photocatalysis: Material
Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 29
2.5 Gold-Modified Semiconductor Photo Catalysis: Photocatalytic
Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.5.1 Titania–Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.5.2 ZnO–Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.5.3 BiVO4–Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3 Black Titania for Photodecomposition of Organic Compounds . . . . . 37
3.1 Introduction: Photocatalyst Technology . . . . . . . . . . . . . . . . . . . . 37
3.2 Titania Photocatalysis: Fundamental Concept . . . . . . . . . . . . . . . . 38
3.2.1 Photocatalysis System: Challenges . . . . . . . . . . . . . . . . . . 38
3.3 Hydrogenated Titania Photocatalyst . . . . . . . . . . . . . . . . . . . . . . . 38
3.3.1 Hydrogenation Process: Fundamental Concept . . . . . . . . . . 39
3.3.2 Hydrogenation Process: Procedures and Parameters . . . . . . 39
3.3.3 Hydrogenated Titania: Basic Concept . . . . . . . . . . . . . . . . 41
3.4 Doped-Hydrogenated Titania Photocatalysis Systems . . . . . . . . . . 43
3.4.1 N-doped Hydrogenated Titania . . . . . . . . . . . . . . . . . . . . . 44
3.4.2 p-Type Doping Semiconductor . . . . . . . . . . . . . . . . . . . . . 45
3.5 Photodegradation Properties of Hydrogenated
and Doped Titania . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 46
3.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 46
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 47
4 Applications of Titania as a Heterogeneous Catalyst for
Degradation of Landfill Leachates . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.1 Introduction: Principle of Organic Compound Decomposition . . . . 51
4.2 Photocatalysis Treatment: Basic Theory and Applications . . . . . . . 52
4.3 Design of Heterogeneous Photocatalysis . . . . . . . . . . . . . . . . . . . 52
4.3.1 Sizing of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.3.2 Structured Modification . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.3.3 Functionalization Approach . . . . . . . . . . . . . . . . . . . . . . . 55
4.4 Photodegradation of Organic Compounds in Landfill . . . . . . . . . . 55
4.4.1 Operation Parameters: pH of Medium . . . . . . . . . . . . . . . . 56
4.4.2 Operation Parameters: Temperature . . . . . . . . . . . . . . . . . . 57
Contents ix
4.4.3 Operation Parameters: Light Intensity . . . . . . . . . . . . . . . . 57

4.4.4 Operation Parameters: Ozone Dosage . . . . . . . . . . . . . . . . 58
4.4.5 Operation Parameters: Catalysis Dosage . . . . . . . . . . . . . . 59
4.4.6 Operation Parameters: Reaction Time . . . . . . . . . . . . . . . . 59
4.4.7 Operation Parameters: Effect of Inorganic Ions . . . . . . . . . 60
4.4.8 Operation Parameters: Dissolved O2 . . . . . . . . . . . . . . . . . 60
4.5 Photocatalytic Activities in Landfill . . . . . . . . . . . . . . . . . . . . . . . 61
4.5.1 Photodecomposition Mechanism of Landfill Pollutant
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 61
4.5.2 Photodecomposition Kinetics of Landfill Pollutant
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.6 Heterogeneous Catalysis: Next Application in Landfill . . . . . . . . . 62
4.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5 Easy Separation of Magnetic Photocatalyst from Aqueous
Pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.1 Overview of Photocatalyst System . . . . . . . . . . . . . . . . . . . . . . . . 69
5.2 Deficiency of Photocatalyst System . . . . . . . . . . . . . . . . . . . . . . . 70
5.3 Preface and Benefits of Magnetic Photocatalysis System . . . . . . . . 70
5.4 Magnetic Photocatalyst System . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.4.1 Magnetic Photocatalyst: Metal Oxide/Metal Composites . . . 71
5.4.2 Magnetic Photocatalyst: Carbon-Based Composites . . . . . . 74
5.4.3 Magnetic Photocatalyst: Ceramic Composites . . . . . . . . . . 76
5.4.4 Magnetic Photocatalyst: Metal Doped . . . . . . . . . . . . . . . . 78
5.4.5 Magnetic Photocatalyst: Nonmetal Doped . . . . . . . . . . . . . 78
5.5 Industrial Relevance of Magnetic Photocatalyst . . . . . . . . . . . . . . 79
5.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6 Solar-Driven, Highly Stable Photocatalyst System for Mitigation
of Organic Pollutants via Mixed Phase Titania . . . . . . . . . . . . . . ... 87
6.1 Introduction: General Concept of Solar-Driven Photocatalyst . ... 87
6.2 Mixed Phase Metal Oxide: Solar-Driven Photocatalyst
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.2.1 Factor of Highly Efficient Photocatalyst Process . . . . . . . . 89
6.3 Development Routes of Mixed Phase Titania . . . . . . . . . . . . . . . . 90
6.4 Physicochemical Nature of Mixed Phase Titania . . . . . . . . . . . . . . 93
6.5 Efficiency and Mechanism of Photocatalytic Activities
of Mixed Phase Titania . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 97
6.5.1 Combination of Mixed Phase Titania (Brookite–Rutile) ... 97
6.5.2 Combination of Mixed Phase Titania
(Brookite–Anatase) . . . . . . . . . . . . . . . . . . . . . . . . . . ... 98
6.5.3 Combination of Mixed Phase Titania (Rutile–Anatase) ... 98
x Contents
6.6 Real Implementations of Mixed Phase Titania in Mitigation

of Organic Pollutants . . ............................... 99
6.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
7 Layered Catalyst Compositions for Photo-Treating of Industrial
Effluents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
7.1 Introduction: Solid Metal Oxide in Photocatalyst System . . . . . . . 105
7.1.1 Preview of Layered Catalyst Composition . . . . . . . . . . . . . 106
7.2 Categories of Layered Catalyst Composition . . . . . . . . . . . . . . . . 106
7.2.1 Hydroxide-Based Catalyst . . . . . . . . . . . . . . . . . . . . . . . . 106
7.2.2 Nanocarbon-Based Catalyst . . . . . . . . . . . . . . . . . . . . . . . 109
7.2.3 Clay-Based Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
7.3 Industrial Applications of Layered Catalyst . . . . . . . . . . . . . . . . . 112
7.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Chapter 1
Enhanced Photocatalytic Activity by Using
Modification Activated Carbon
Samira Bagheri and Nurhidayatullaili Muhd Julkapli
1.1 Introduction: Basic Principles of Heterogeneous

Photocatalysis System
The published articles have specified the background in theory and environmental
supplication in heterogeneous photocatalysis system for semiconductors.
One of the main limitations of utilizing semiconductors is the power necessity
due to the ultraviolet light usage (Huang et al. 2014), although upgrading the pho-
tocatalytic systems may elevate the reaction rate and henceforward reduce the time
of residence and minimalize energy consumption per unit of volume being treated.
This might be accomplished by the photocatalysis material deposition on high surface
area materials, which will particularly absorb the polluted molecules and will fixate
them around the photocatalysis particle. These limitations have helped researchers
to find any worthy initiative of semiconductor for the operation of some particular
pollutants, or try to formulate latest techniques of deposition. The pH of the solu-
tion, the support, and the kind of pollutant plays a significant role in the exploit of
photocatalytic process.
Many efforts have declared the usage of activated carbon as a catalyst support
for the semiconductor but it has been alerted that effective absorption of pollutants
into the absorbent area may hinder diffusion to the catalyst and thus may affect the
entire process (Quiñones et al. 2014). The employment of activated carbon like a
brace for the titanium oxide (titania) turns out to give greater tremendous above the
other mediums, due to its potential to absorb pollutants, also, its high absorption
capability due to its high surface area and decent porosity. As specified, medium
pores of activated carbon will ease the diffusion of pollutants and product discharging
S. Bagheri (B) · N. Muhd Julkapli

Nanotechnology and Catalysis Research Centre, University of Malaya, Kuala Lumpur, Malaysia
e-mail: samira_bagheri@um.edu.my
N. Muhd Julkapli
e-mail: nurhidayatullaili@um.edu.my
© Springer International Publishing AG, part of Springer Nature 2018 1

S. Bagheri and N. Muhd Julkapli, Nanocatalysts in Environmental Applications,
Green Energy and Technology, https://doi.org/10.1007/978-3-319-69557-0_1
2 S. Bagheri and N. Muhd Julkapli
from the surface. Additionally, the high ability of activated carbon to absorb fluids
may reduce the penetration of ultraviolet lights into small areas, and it may cause
confining of pollutants within the pores without getting able to diffuse into the outer
surface for further reaction with the pollutants OH radical. Furthermore, some kinds
of pollutant, such as phenol, may start polymerization on the AC’s surface, which
can cause unchangeable absorption.
1.2 Activated Carbon
1.2.1 Characterization of Carbon Nanomaterials
Lately, carbon nanomaterials technology has made unexpected development due to

its variety of physicochemical properties, such as exciting electronic properties, elec-
trical conductivity, tunable porosity, lightweight, chemical and thermal balancing,
and the potential to acquire an immense range of morphologies (Poonjarernsilp et al.
2014). Henceforth, carbon materials have found a large number of applications in
different domains, varying from environmental science, absorbent, drug delivery,
catalyst, electrode materials, stationary phase in the chromatography system, energy
storage, and many others. However, for some particular applications, functional-
ization is essential at controllable size and shape. Nevertheless, the production of
such materials usually requires very harsh conditions and has several limits such as
extreme temperature of the carbonization process in the first step up to (>800 °C)
and followed by chemical or physical activation to transform carbon materials into
activated carbon. Furthermore, it is significantly important here to explore economi-
cal and sustainable ways to get carbon materials from raw materials other than crude
oil or natural gas lead to a re-exploration of this field
1.2.2 Transformation of Biomass to Carbon
Biomass conversion to carbon materials through catalytic approach normally begins

with hydrolysis of dehydration and cellulose chains and divided into monomer’s
soluble products that come from the hydrolysis of cellulose, condensation or poly-
merization of the soluble products, aromatization of the polymers hence formed, and
growth of the nuclei so created by linkage and diffusion of species from the solution
to the nucleus surface and finally appearance of short burst of nucleation.
1 Enhanced Photocatalytic Activity by Using Modification … 3
1.2.3 Catalytic Transformation of Biomass to Carbon
Green chemistry, nowadays, is becoming more and more connected with the catalytic
process on biomass conversion to carbon materials.
1.2.3.1 Homogeneous Catalyst
The solvents of catalyst as ionic liquids have received enough attention because of its
low vapor pressure, stability, and recyclability (Liu et al. 2013). The kinds of novel
green solvent are ionic liquids with the relatively less melting point and appear as
a crystal in general conditions. Cellulose is balanced via inter- and intramolecular
bonds of hydrogen, so that rigid bundles could be created, which makes it difficult
to solubilize with common organic solvents and water. Ionic liquids have significant
roles; it acts both as a soft template to formulate the characterized pore structuring
for the development of a hierarchical porous carbon structure and as a catalyst which
results in enhanced ion thermal carbon yields (Wei et al. 2011). Thus, it has been
demonstrated that in the presence of an acid catalyst, the utilization of ionic liquids
can embrace the efficiency of the hydrolysis of glucose cellulose (Yang et al. 2012).
1.2.3.2 Heterogeneous Catalyst
The utilization of heterogeneous catalysis along with an immense range of designs

is less expensive and extraordinarily stable at high temperature. This method has the
benefit of being very economical and mild if we follow some rules of green chem-
istry since it does not add organic solvent with resulting carbon, which is spherically
shaped and the surface is decorated with oxygenated functional groups (Sevilla and
Fuertes 2009). This method also involves simple reaction mechanisms for the cre-
ation of carbon, which involves the dehydration of carbohydrate into a furan like
molecules, mainly 5-(hydroxymethyl)-2-furaldehyde as an initial step and further
polymerization and carbonization as a next step. This reaction possesses a high
potential for the catalytic improvement biomass since –C–C– coupling takes place
with consistent oxygen removal (the reaction involves the dispatchment of CO2 and
water) from carboxylic acids, the latter of which are mutual intermediates in the pro-
cess of biomass conversion. If we compare homogeneous catalysis, carbon materials
obtained through a heterogeneous catalytic process consist of an aromatic core con-
taining polyfurane-type units which is surrounded by oxygen-rich polar functional
groups such as COOH, –OH, –C–, and –O–, make the materials more hydroscopic
and hydrophilic, and have a lesser degree of graphitization.
Nevertheless, the effective exploitation of cellulose is a main challenge in het-
erogeneous catalysis application, since cellulose itself has a tough, mainly crys-
talline, chemically stable and water insoluble characteristics, which are induced from
the intra–intermolecular hydrogen bonds. The most commonly used heterogeneous
catalyses for the conversion of biomass are alkali salts, metals (Ni, Rh, PT, Ru, Pd, Ir,
and Ag), metal oxides (CeO2 , ZrO3 titania, and Al2 O3 ) usually on supports, and metal
oxide catalysts at medium temperatures (300–425 °C) which involves deoxygenation
reaction combined with –C–C– coupling processes (Tong et al. 2010).
Solid Acid Catalyst
Solid acid catalysts have various benefits over liquid acid catalysts as it facilitates the
separation of product that eventually can be recycled without losing the activity and
it minimizes the cost of post-treatment such as neutralization and effluent processing;
it can even work at higher temperatures, therefore reducing the reaction time. Solid
acid catalysts are basically a Bronsted or Lewis acid and it is of various types such
as Vanadyl phosphate, ZrO2 , zeolites, inorganic oxides, and ion-exchange resins.
Bronsted or Lewis Solid Acid Catalyst These series of Lewis catalyst including
WOx /ZrO2 , C–Al2 O3, Zr–P, SiO2 –Al2 O3 , and HY zeolite are used for mainly aqueous
phase dehydration of xylose (Li et al. 2015). Few studies have characterized the
concentration of both Lewis and Bronsted acid set of these series of catalyst with
FTIR and TPD spectroscopy by using gas-phase NH3 and compared the catalytic
selectivity and activity with homogeneous catalyst activities for the dehydration of
an aqueous solution of xylose. The catalyst selectivity is a principle of the Bronsted
to Lewis acid site ratio of the heterogeneous reaction (Nandiwale et al. 2014). Lewis
acid sites lower furfural selectivity through catalyzing a side reaction. In the hot water
(190 °C), solid Lewis acids promoted the cellulose depolymerization and lowered
the creation of soluble oligomers and polymers as in connection to the cellulose self-
hydrolysis which occurred in the familiar conditions (Cheng et al. 2011). By contrast,
in normal conditions, strong Bronsted solid acid has not improved the extent of the
cellulose depolymerization but has affected the product distribution. It has been
discovered that the normal product of soluble Bronsted acid catalyst in cellulose
depolymerization like glucose and HMF was not generated through the conversion
process but lactic acids and levulinic were accepted (Weingarten et al. 2013). If we
compare, Lewis solid acids were not only potential to upgrade the extent of cellulose
depolymerization but also favorable for direct formation of lactic acid, which gives
high yield, approximately 30%. This comparison represents highly potential ways
to optimize the conversion of cellulose and stabilize Bronsted acid catalyst which
helps to understand the reaction pathways (Zhao et al. 2011).
This also brought an idea for various researchers to study the effect of Bron-
sted acidities of water-soluble heteropoly acid catalyst, known as HPA. This het-
erogeneous HPA catalyst is micellar, clean, economical, facile, and environmen-
tally friendly process which could be recycled via centrifuge (Hu et al. 2012). The
exhibiting activity for the hydrolysis of polysaccharides comprising disaccharides,
starch and cellulose, is known to be HPA. Tungstophosphoric acids (H3 PW12 O40 )
and tungstosilicious (H4 SiW12 O40 ) are the vigorous acid used in the series of HPA
as a catalyst in reaction of hydrocarbons and has been employed for example, in
alkylation, acylation, esterification, dehydration, and isomerization of the ethanol

process. Salt of acidic cesium H3 PW12 O40 , Cs2.5 H0.5 PW12 O40 (Cs2.5 H0.5 PW) with
intense acidity is insoluble in organic solvents and water, and has meso- and micro-
pores with relatively high surface area (130 m2 g k). This Cs2.5 H0.5 PW has been
described as a solid acid catalyst with prudent and environment-friendly specifica-
tions, and is recommendable in industrial process like hydration of olefins or ester
and liquid-phase dehydrated alcohol. Till now, cellulose hydrolysis into saccharides
employing a range of HPA catalyst has been researched for capable applications,
in contrast to conventional acid-catalyzed reaction, whereas the yield of glucose is
less (Patil and Lund 2011). It is because of the insolubility of cellulose in any of
solvent and problems of solid to solid mass transport. In a few cases, the acidity of
mineral acid is lower than that of HPA. For example, (H0 ) of H5 BW12 O40 (0.7 M at
100 °C) the Hammet acidity function is −2.1 lower than those of HCl (0.7 M) and
H2 SO4 . Hence, HPAs have been anticipated to be reusable and active catalyst for
the hydrolysis. Along with that theory, amorphous carbon-bearing SO3 H, COOH,
and OH groups had been described to show hydrolysis activity (10% of glucose
yield) for 3 h at 100 °C. Meantime, Yabushita et al. demonstrated that the cel-
lobiose hydrolysis and cellulose in water assisted by HPAs such as Sn0.75 PW12 O40 ,
H3 PW12 O40 , and H4 SiW12 O40 records total yields of decreasing sugar and it was
around 40% at 200 °C for 16 h of reaction (Yabushita et al. 2014). It has been
founded by Hara that H5 BW12 O40 exhibited a good performance for the transfor-
mation of crystalline cellulose to give glucose 77% yield and various types of HPAs
like H3 PW12 O40 (glucose yields 8%) and H4 SiW12 O40 (37%) which are less active
than H5 BW12 O40 . Other research groups also administered the screening of counter
cations of PW12 O40 for the cellobiose hydrolysis and they found that there was a
volcano-type correlation between Lewis acidities and TOFs for glucose formation
(Chambon et al. 2011). They also observed that the acidity and the role of decreas-
ing CrI were the significant factors for the catalytic activity of HPAs. In reality, the
H0 role was H3 PW12 O40 < H4 SiW12 O40 < H5 BW12 O40 in the similar order of cat-
alytic activity. The H0 roles were corresponding to the concentration of acids and the
number of anions. Hence, HPAs involving highly negatively charged ions which are
desirable. The anions were dissociated from hydrogen-bonding between cellulose
molecules to lower the CrI. Moreover, HPAs protons have also exhausted the bonds
of hydrogen from cellulose and greater concentration of protons was effective in this
role. Therefore, a strong catalyst for the cellulose hydrolysis is H5 BW12 O40 , which
was recovered through the extraction and it was recycled for around 10 times.
Ion-Exchange Resins Sulfonic acid functionalities of ion-exchange resin with solid
acid catalyst and sulfonic acid functioned materials resulted in high yield at 63 and
76% in pure dimethyl sulfoxide (DMSO) solvent, correspondingly (Lee et al. 2014).
Solid acids such as amorphous carbon materials consisting of SO3 H groups layered
transition (HNbMoO6 ) metal oxide and resin sulfated have been tested for the cel-
lulose hydrolysis, but the yield of glucose is still comparatively less. It has been
hypothesized that side reactions were abolished employing aprotic or organic sol-
vents (Johnson and Panas 2000). Vigorous acidic resins (Amberlite IR-200 and IR-
120), niobic acid, mixed oxides (silica–zirconia and silica–alumina), silica–niobia,

and niobium phosphate created a strong acidity which was protonic, and accessibil-
ity of simple saccharides to the most effective sites on the surface catalyst allows
satisfactory reaction rates to be obtained (Suganuma et al. 2008).
Sulfonic resins, which are acidic, are represented in different literatures as active
system of catalytic for the hydrolysis of starch, cellulose, and disaccharides (Shimo-
mura et al. 1967). Generally, the rigid conditions in terms of temperature (>120 °C
temperature in the water and in critical condition) and high concentration of saccha-
ride (>100 g) were employed to push the catalytic actions of solid acid toward the
achievement of high transformations (Igarashi 2013). Sulfonated activated carbon
could transform cellulose of amorphous into glucose with 41% of yield for 24 h at a
temperature of 200 °C. Such things have been founded by Sun and Zhang Schaller
who demonstrated that p-toleunesulfonic acid can catalyze cellulose hydrolysis in
ionic [EMIM][Cl] system, giving THF yields of 28 and 13% and a yield of mono-
and disaccharides 10 and 3%, respectively (Heinze and Gericke 2014). Natural bam-
boo can be converted by a sulfonated biomass char with cotton and starch around
20% yield of glucose under microwave assistance (Koller et al. 2015). The process
of hydrolysis consisting of starch and cellulose was obtained via layered transition
metal oxide, despite the yield from glucose was less than cellulose. Sulfonated car-
bon with a mesoporous like structure was used by the groups of Vyver for cellulose
hydrolysis getting the yield of glucose around 75%, which is considered to be high-
est recorded yield via solid acid catalyst. Similarly, some interest has been shown in
cellulose depolymerization in water because solid-supported acid catalysis was used
(dos Santos et al. 2013).
Current reports describe the cellulose hydrolysis by solid catalysts such as lay-
ered transition metal oxides, Amberlyst resin acid modified amorphous carbon and
sulfonated silica or carbon nanocomposites (Lee et al. 2012). Also, the cellulose
depolymerization of cellulose was considered under catalyzed of both FeCl3 and
nafion supported by amorphous silica to be tested on a continuous flow reactor,
given the residual that unreacted cellulose can be easily eliminated from the system.
For the conversion of glucose, these surface species which are acidic were quite
active. Certainly, we are aware that the hydrolysis rate of cellulose depends on the
acid strength. As an expansion on previous reports usage of nafion as a solid-assisted
acid catalyst for the transformation of cellulose into glucose and levulinic acid,
many researchers have incorporated the reaction with alkali metal salts to embrace
the reaction’s yield (Akiyama et al. 2011). Klamrassamee et al. and Namchot et al.
have recently formulated carbon-based solid acid with immense density of Bronsted
acid sites (SO3 H and COOH) to pyrolytically carbonize sugar, such as cellulose,
sucrose, or glucose and subsequently sulfonate the prepared carbons (Weerasai et al.
2014). Interestingly, these sulfonated carbon materials are very strong for the micro-
crystalline cellulose hydrolysis to produce water-soluble saccharides at low reaction
temperature (100 °C) with the conventional and strong Bronsted acid catalyst such
as H-mordenite, niobic acid, and others. The particular surface area of the sulfonated
carbon was around 2 m2 g−1 but the soluble saccharides yield reached nearly 70%.
Catalytic performance of soluble saccharides was applied to its intrinsic ability to
adsorb β-1, 4-glucan, which is not absorbed on the other solid acids. Thus, it can be
concluded that heterogeneous catalysis is more active and environmentally benign,
mainly because of a hasty product separation and also catalyst recovery. Takagai
et al. described that acid resins with considerably big pores could actively depoly-
merize cellulose in ionic liquid, but the main products were cellooligomers which
were failed to be dissolved in water (Masters and Maschmeyer 2011).
Zeolite Catalyst
Crystalline microporous solids are an important part of zeolites because of its

widespread application in absorption, separation, and catalysis. Its important
stems from its unique structures of pores, which makes it highly particular to
absorb molecules for separation reasons or toward product molecules in catalysis
(Chen 1996). Furthermore, during heterogeneous catalytic reactions, it shows good
hydrothermal and thermal stabilities. However, from the last 20 years, there have
been many studies that focused on the catalytic transformation of biomass and its
derived feedstocks with a variety of zeolite catalysts, including Ferrient, FCC, Al-
MCM-41, ZSM-5, Beta zeolite, Y zeolite, SSZ-20, IM-5, TNU-9, MOR mordenite,
SBA-15, Al-MSU-F FER, ZSM-23, MCM-22, and MFI (Louis et al. 2011). ZSM-11
and ZSM-5 among these series had the lowest amount of coke and the highest yield
of aromatic because of its pore space and steric effects. Manufacturization of ordered
porous carbon material has been obtained previously through replication of ordered
zeolite inorganic and nanocasting. Inside zeolite, many reactions have occurred which
includes decarbonylation, dehydration, isomerisation, and decarboxylation and with
that removing oxygen as carbon dioxide, water, and carbon monoxide and conver-
sion of carbon and hydrogen into aromatics and olefins (Azeez et al. 2011). In these
catalysts of zeolite, ZSM-5 has exhibited the highest olefin and aromatic yields from
biomass of lignocellulosic. With a pore size of around 5.5–5.6 A, ZSM-5 has a
three-dimensional pore system. This small size of pore, internal volume, and inter-
nal structure has made it problematic for greater aromatic coke antecedents to form
inside the pores (Mante et al. 2013).
Metal Ion Catalyst
Furfural and HMF are the two main and significant intermediates which are derived
from biomass. They were directly manufactured from the microcrystalline cellulose
hydrolysis with metal ions in ionic liquids such as Fe3+ , Fe2+ , Cr3+ , Co2+ , and Mn2+
as a catalyst under mild conditions (Williams et al. 2012). Metal ions as an acidic
support are a nice catalyst for hydrogenation and ring opening of cellulose polymers.
Many reports are there on carbon production through cellulose hydrolysis at a
moderate temperature up to 250–300 °C metal catalyst in a very less reaction time
to control the deep exploitation of the formed glucose (Vuyyuru and Strasser 2012).
Some researchers even used Ru that is a ruthenium catalyst to enhance the transfor-
mation of oligosaccharides and increased glucose yield (almost 30%) with the TON
that is the turnover number of the catalyst was immense (145 based on bulk Ru) in
contrast to those of the sulfonated catalysts of carbon (Dreher et al. 2013). Wang
et al. 1993 founded that the glucose yield was increased around 31% by upgrading
the Ru loading to 10 wt% along with the recyclable amount of catalyst up to five
times without losing the activity or Ru leaching (Wang et al. 2012). Various reports
on the efficiency of the hydrolyzed cellulose formulated by Ru catalysis as sources of
carbon for the bacterial PHA production and founded that, under the aqueous solu-
tion the reaction which occurs is desirable for delivering to microbes which there
upon makes it easily disconnected from yielded sugar via facilitating the race of the
catalyst and filtration (Ashik et al. 2017). Such reports have accepted that Ru species
were in fact in an oxidized state acted as the real and effective site for the oligosac-
charides hydrolysis. Prior, Ru/Co3 O4 catalysts have showed considerate selectivity
and activity and good recyclability in the biomass conversion to carbon.
Metal Oxide Catalyst
In many catalytic processes, metal oxides play an important role. For example, metal
oxide nanostructures are important component which are commercially available
for synthesis of methanol (Liu et al. 2016). There are many more benefits of these
catalysts which make them efficient candidates for green processes. The charac-
teristics of such catalysts are stable, nontoxic, low cost, availability, nonvolatility,
and reusability. Several studies have observed the processes of decomposition con-
nected with formic acid on nano-metal oxide surface, methanol, and formaldehyde.
It is strongly expected that metal oxide nanostructures would have a better catalytic
activity in developing the conversion of cellulose to the value-added products in
hydrothermal media with an efficient separation from the reaction matrix in regard
to the increased surface area of the nanomaterials (Li et al. 2013). Layered transition
metal oxides containing niobium found to be specifically active in the hydrolysis of
disaccharide, suggesting the importance to investigate niobium containing catalyst
as an energy-inefficient factor for the conversion of biomass.
The employment of transition metal oxide like HNbMoO6 was also reported as an
efficient solid catalyst to generate glucose from cellulose. Similarly, in the presence
of noble metal consisting of catalyst, for example, Pt/Al2 O3 , Felice et al. have found
the creation of sugar alcohols in yield up to 31% from cellulose in hydrothermal
conditions. On the other hand, the researchers proclaimed that Pt-free catalysts have
generated only poor glucose hexitols amount.
1.3 Photocatalytic Systems with Activated Carbon
The activated carbon is a carbonaceous material, which structured on plant-based

material, is a porous, amorphous solid carbon. Well-developed porous surface, pro-
vided with high pore volume and extended surface area, makes activated carbon the
most commonly used technique for controlling pollution. Well-developed pores over
the surface are one of the main uses of activated carbon as the photocatalysis sub-
strate. Nontoxic, chemical stability, and being economical are the main reasons that
in past decades the heterogeneous technology has got many attentions (Khan et al.
2014). As the organic pollutants can be mineralized into neutral by products such as
H2 O, CO2 , and mineral acids, one of the main properties of heterogeneous-activated
carbon photocatalysis methods includes the destruction of the wider category of
organic compounds. Promoting solar radiation and working on the low temperature,
eventually saving a lot of energy, make it very economical. One of the advantages
of the activated carbon includes the regeneration of spending absorbent, and demol-
ishing of absorbed organic material on the site is converting the loss of absorbents
to burn them concluding that thermal regeneration is efficient (McEvoy et al. 2013).
Activated carbon, being the strong light-absorbing compounds, has been success-
fully used as photoactive species. Determining the band gap of the activated carbon
(band gap less than 4 eV) resulted in being a semiconductor and therefore as photo-
electric materials in the presence of ultraviolet radiations (Khan et al. 2014). Recent
reports suggest the abnormal reaction toward the aqueous environment by directing
ultraviolet irradiation of the sample in the presence of the activated carbon provided
that no other photoactive materials are present showing that the activated carbon
improved the photo-oxidation of phenol, beyond the degradation of photolysis in
comparison to bare or unmoved titania (Velo-Gala et al. 2013). To find the difference
whether this reaction is only shown by the activated carbon or also by other car-
bon compounds, some researchers have worked on different porous activated carbon
materials obtained from different sites, procedures, and reactions and their behavior
to the exposed ultraviolet radiations (Pamecha et al. 2016). The final solution is to
remove any vagueness in result that in aqueous medium, ultraviolet radiations, and
absence of semiconductor activated carbon are able to demolish the organic mate-
rials in the respectiv conditions. Regardless of the type, activated carbon acts as a
catalyst during removal of diatrizoate. Gamma radiations based on activated carbon
is more efficient in a way that it is a higher proportion of C atoms and contains
sp2 hybridized (Nishida et al. 2004). With more than 53% of synergistic effect in
diatrizoate in the first minute of reaction, commercial carbon exhibits it from the
ultraviolet/activated carbon system. Providing more oxygen, the synergistic act of
activated carbon is boosted up. The reutilized activated carbon is quite similar to
original C; the presence of O in the sample increases the rate of removing of dia-
trizoate by the ultraviolet/activated carbon system, but the ultraviolet inclusion of
system results in some modifications in activated carbon chemically. There is a very
vague relationship between the textual properties and the synergistic contribution of
the activated carbon. Gamma radiation involvement with activated carbon reduces
the band gap that results in more efficient removal of organic compounds. One of the
actions proposed in the results and evaluations that the activated carbon is the pho-
tocatalysis substrate which will promote the electrons from the valence band to the
conducting band, resulting in enhanced generation of OH-free compounds present
in the polluting medium.
1.3.1 Effect of Surface Properties
Many researchers and authors reported many surface and textual features of acti-
vated carbon. It is clear that basic activated carbon in the presence of low oxygen
in this medium is much more potential of the phenol adsorption. An increase in the
physical absorption and surface polymerization of phenols can be done by ensuring
the deprivation of the acidic categories on the surface of the activated carbon. Irre-
versible absorption and catalyzing the oxidative coupling of phenolic compounds
can be enhanced by the O2 containing basic categories over the face of activated
carbon. Boosting up the interactions between π–π electrons in activated carbon and
phenols is due to the graphene layers of an activated carbon, which increases π elec-
tron density (Elangovan et al. 2015). In carbon of basic nature, phenol is considered
to be higher because of being, regardless of textual properties, absorption capacity.
Retention of phenol is supposed to become less in the acidic carbon as compared to
the basic carbon; in fact, there is no clear relationship between two.
One of activated carbon drawbacks is that the waste organic materials not really
destroyed but are transformed from one phase to another and in result the used
activated carbon is transformed into a dangerous product. So, regenerating activated
carbon becomes necessary for its reusability, which makes an economical process.
The activated carbon is carrying some limitations like its adsorption capacity, which
is a function of inert concentration that results in low-quality products (Babadi et al.
2016). Already used activated carbon is to be disposed of as it is hazardous material
or regenerated to be used again. Thermal regeneration contains many disadvantages
because of its off-site regeneration that hardly converts the pollutant from one phase
to another. This may result due to depletion of carbon and may cause damage to the
structure of activated carbon.
The process, which could produce high yield efficiencies, could be a chemical
regeneration of spent activated carbon but it has some drawbacks regarding chem-
ical consumption nondestructive pollutant elimination and creation of unimportant
steams of waste (Eliyas et al. 2013). However, techniques like ultrasonic regenera-
tion, microwave regeneration, and electrochemical regeneration are also being pro-
posed as alternative techniques for the process of chemical regeneration of spent AC.
Due to the limitations of the present technique, there is a need to develop another
technique, which is more economical and environmental friendly. Thus, to make
one hybrid system, there is a need to merge semiconductor with activated carbon.
Organic pollutants, issues of destruction, and other hazardous problems are expected
to arise from the oxidation semiconductor element. The reason lies in the genera-
tion of radical species like O• and OH• from the catalyst particles of semiconductor,
which causes oxidation of such species. Another technique that has been studied for
activated carbon is the combination of heterogeneous photocatalysis and the Fenton
reaction with the catalytic process, which is an oxidation-based process.
Studies on this spent activated carbon, which carried out previously, were mostly
about granular AC. Take an example which demonstrated that there was improved
efficiency in herbicide removal from the water when granular activated carbon
adsorption photocatalysis substrate hybrid system was used in comparison with a

photocatalysis system (Babadi et al. 2016). Similarly, it was also reported that the
combination of photocatalytic and rotating adsorbent showed better efficiency in
removing formaldehyde in comparison with adsorption (Xu et al. 2014).
1.3.2 Activated Carbon/Transition Metal Oxide

By impregnation and adsorption along with various methods, metal oxides are
expected to be impregnated into the surface of carbon; all the same, this is applied
for complex experimental procedures and process, which operate at high tempera-
ture. Considering ideal conditions, a photocatalysis material should be inexpensive,
highly proactive, and nontoxic and stable. One more criteria that play a role in the
degradation of organic compounds is that the potential of the redox resides in the
band gap of the semiconductor. There are many semiconductors with the band gap
energies ample to catalyze several chemical reactions, which include WO3 , Fe2 O3 ,
SrTiO3 , ZnS, titania, and ZnO (Yang and Bai 2014). The metal sulfate group with
insufficient stability in the process of catalysis is kids, PbS, or CdS. This compound
undergoes photo-anodic corrosion readily and is toxic. For example, Fe3 O4 under-
goes photo-anodic corrosion readily so they are not suitable. ZnO (3.2 eV) is unstable
with Zn (OH)2 in water, and also it has a band gap similar to anatase, so it results in
the deactivation of the catalyst.
1.3.2.1 Activated Carbon/Titania Photocatalysis System
Titania Photocatalysis System
The most promising semiconductor for photocatalytic destruction organic pollutants

is titanium dioxide (titania). It provides the most excellent agreement in aqueous
media between stability and catalytic performance. Since it is nontoxic, cheap, bio-
compatibility, and stability in sunlight, it is of immense importance; that is why it is
also considered usable cleaning environmental operations. Consequently, the elec-
tron pairs and positive holes are created at the surface of titania. Once it has been
irradiated with the UV light of the wavelength of 380 nm, titania would form reactive
oxidants, e.g., OH radicals, hydrogen peroxide, superoxide anions, and other reac-
tive species of oxygen and reactions that are reductive, to contribute in the organic
compound decomposes which are adsorbed on the surface of titania (Zhang et al.
2014a, b). The highest photocatalytic detoxification of titania is anatase phase. Deep
studies have shown that photo-degenerations of components like herbicides, phenols,
dyes, pesticides, surfactants, and organic components (e.g., salicylic acid and sulfos-
alicylic acid) have been possessed by titania that is present in water wastes. titania
powders contributed to some drawbacks in separating phase in photocatalysis, with

purpose of its emission in the atmosphere because of their small size of the particles
and recovery, the loss of photocatalysis substrate if the separation is not promising,
the need of fluidization of the powder in gaseous phase with cost and energy, and the
scaling difficulties involved (Amir et al. 2015). Also, since radiation from the light
compromises 47% visible light, 48% infrared radiation, and 5% UV light, titania
acts as a benchmark of UV photocatalysis that it goes deactivated under visible light
because of its wide band gap (Amir et al. 2017). Moving on, the holes and photo-
generated electrons present in an excited state play a vital role in the degeneration
of pollutant and are unstable; and without any effort it can recombine and it leads
to low-order efficiency results of photocatalysis activities. It is clear that the use of
high potential solar photocatalysis cannot be made by titania.
Titania/Activated Carbon Photocatalysis System
For easy manipulation in a process of total photocatalytic operation and quick decom-
position of organic pollutants, it might speed up the process to load photocatalysis
to suitable adsorbents to increase the strength of pollutants around the photocataly-
sis system. Therefore, researcher had made attempts to support titania on different
matrixes as silica gel, clay, carbon materials, alumina, and zeolites which can be
nanotubes, carbon microspheres, carbon black, carbon nanofibers, and activated car-
bon (Zhang et al. 2010). Titania particles are hydrophilic when exposed to direct
UV light, whereas organic pollutants are hydrophobic. The use of activated carbon
as a reference will provide help to molecules of pollutant closer to the active site of
titania for a quick and effective photo-degeneration process. The activated carbon
to favor organic pollutants that are approaching, in which secondary degradation to
take place intermediately in situ can generate new adsorption centers.
In gas and water remediation for support purposes, activated carbon is used widely
because of its high porosity, good adsorption, supported titania, and low cost that
has marked the effects on disappearance of pollutants kinetics, with each pollutant
being more quickly degenerated. For example, the titania surface is made static over
glass surface; it has the benefits like high photodegradation productivity. The major
limitation is the adhesion force in titania membrane and glass is poor, so titania is
easy to decrease, which causes the decrease of the photodegradation productivity.
Hybrid of titania with activated carbon support, as a sensitizer which is able to
absorb light, was proven to be the best approach to develop photo responding pho-
tocatalysis material with great activity. The formation of heterojunction between
titania with a small band gap and negatively charged activated carbon may result in
the inoculation of conducting band electrons from activated carbon to titania and it
is very useful for electrons and hole division. At the same time, the immobilization
of titania onto the activated carbon support can compromise for the loss of photo-
catalytic ability of titania because of the difficulty to effectively disperse in water
for complete interaction with pollutants. So, many researchers reported that there is
an optimum titania that uses amount and activated carbon pore formation for attain-
ing the higher photocatalytic productivity than titania (Bagheri et al. 2012). The 3-D
relation between the particles of activated carbon, titania as a photocatalyst substrate
with small particles, and the molecules of organic toxic is reported to be represen-
tational in the absence of light and in the presence of ultraviolet enlightenment. The
organic pollutants are supposed to be small to adsorb in microspores. In most of the
activated carbon, a large group of micropores exists over the broad surface of the
substantial pores, mesopores and macropores; a large amount of toxic particles is
well balanced due to physical adsorption (Zhang et al. 2012). Instead, only a little
number of pollutant particles are adsorbed on the surface of titania. By depositing
titania molecules onto activated carbon particles, some mesopores and micropores
become closer to their openings and this causes a marked lessen in the uncovered
surface area. The ultraviolet enlightenment over such titania used activated carbon
molecules; oxidative OH-free radicals take birth on the titania and can destroy toxic
molecules by oxidation.
The moving force of migration is actually the saturated gradient between organic
toxic particles over the enlightenment of titania interface and on the other side
some over the surface of changing pore sizes of the activated carbon molecules.
The molecules diffused inside micropores of activated carbon migrate with greater
retaliation toward titania molecules resided on the interface of the activated carbon
particles. Thus, highly microporous-activated carbon particles are not usually advan-
tageous for the titania: activated carbon to have preferred the photocatalytic response
(Bagheri et al. 2012). The effect of the substrate pore skeleton has been observed
using activated carbon surface area (770–1150 m2 g−1 ) and a dip-hydrothermal pro-
cess of photocatalysis material preparation. Improved photocatalytic demoting of
methyl orange (MO) has been attained with titania: activated carbon than with a
simple mixture of titania and activated carbon.
This got into the design of highly effective titania: activated carbon hybrid het-
erojunction photocatalysis substrate, and also the demand of commonsensible cross-
check capacity of band potentials among hybrid modules, the spatially and flat acces-
sible transmission of holes and electron at the exposed surface, and the hole and
electron movement of the hybrid system are important to enhance the photocatalytic
action. It has been reported that the surface chemistry and map of activated car-
bon revealed major effect on the collection of titania particles and photocatalytic
deprivation of 4-chlorophenol. Adding to this, some researchers have constructed
titania with activated carbon microspheres to both maintain spreading and speeding
up separation due to the activated carbon microsphere that can be balanced with
airy bubbly and it can be speedily settled in the reactor base with the help of some
gravity due to the air bubbles. In addition, some authors have fabricated titania with
activated carbon microspheres to both sustain spreading and acceleration division,
because activated carbon microsphere can be balanced with air bubbles and be able
to speedily settle on top of the reactor base by gravity due to air bubbly. To overcome
this shortcoming, the use of co-binder upholding the expansion of another method
to obtain a fresh form of the titania: activated carbon photocatalysis system for such
a high action and better division performance.
Therefore, most samples which were cooked at higher temperature were very
detrimental to photoactivity. Also, using different types of activated carbon revealed
the connected effects between titania and activated carbon during the 4-chloro-phenol
photodegradation and found a clear enhancement of photoactivity due to an increase
in electron density of the activated carbon support (Kuo et al. 2014). It is researched
that attendance of activated carbon in interaction by titania helps due to its burly
adsorption capability. In the same way, it advances the relocation rate of the interfa-
cial change as well as lessen the rejoining rate of the holes and electrons (Jung et al.
2013). This synergistic effect of the interaction of activated carbon and titania has
been previously been stated for deprivation of some organic compounds in the pho-
tocatalytic process. It has been credited to a common contact between the different
solid phases, in which activated carbon acts as an efficient adsorption agent for the
organic pollutants.
The organic more efficiently moved to the titania surface, where it is immedi-
ately photocatalytically degraded by a mass movement of the photoactivated titania.
Thus, the organic burning rate observed on titania: activated carbon is like heading
both with surface diffusion toxin particles and with the photocatalytic process rate;
because adsorption occurs gradually, the variation in relative pollutant proportion
with irradiation time depends on both adsorption and photodecomposition, mainly
at the start of ultraviolet treatment. It is stated that the variance of the proportion
of phenol (as model of organic pollutants) remaining in the solution by ultraviolet
treatment time is compared for titania: AC, which were prepared by hydrolysis of
tetraisopropyl orthotitanate and heat treatment at 650–900 °C. For example, it is noted
that, in the duration of first 1 h, adsorption of pH occurs in native-activated carbon
and after 3 h, in the presence of UV irradiations, saturation is achieved. Adsorption
as well as the photodecomposition of pH takes place simultaneously, but on the other
side the former is supposed to become the dominate method in the beginning, simi-
larly latter in the next stage. The noted trend was based on two linear processes; the
change of one process to the another takes place approximately in 1 h of irradiation.
Design of Material
A number of methods are available for the composition of titania: activated car-
bon catalyst, such as precipitation, chemical vapor deposition (CVD), hydrothermal,
aerosol pyrolysis, hydrolysis, dip coating, and sol–gel. However, selection process
which is used for the selection of a suitable impregnation method depends only on
support used in it and the pollutant which is degraded. It is clear that those physico-
chemical properties of titania: activated carbon catalyst have a heavy impact on the
structure of the supported catalyst, and it depends basically on the preparation method
used, for example, thermal treatments. The main advantages of using physical meth-
ods are simple, low cost, and the use of commercially is present in photocatalysis
material with the wanted functionalities. By using the wet methods the hybrid of
titania: activated carbon was also being prepared, the mismatches in the level of lat-
tice among two hybrid components lessen the required efficiency of separation and
transmission of photo-generated carries (electron and hole) (Li et al. 2012). Adher-
ence of activated carbon surface to titania particles appears significant for increment
of photocatalytic action and as well for useful applications of hybrid system. To
increase the anchorage of titania on activated carbon, the wet process of synthesis is
warranted. This is only because the physical stable hybrid of titania: activated carbon
in disagreement with hydrodynamic shearing method, surface chemistry plus acti-
vated carbon pore structure can have a sufficient impact overspreading of titania over
the synthesis; it results in the different photocatalytic presentations of titania: acti-
vated carbon. Nevertheless, titania photocatalysis substrate usually has low precise
surface region. Due to crystallinity development which happens in heat operation
like that. To prevent titania sintering, or else to make it precise surface region better,
activated carbon can be examined like a better help for the photocatalytic materials
(Gondal et al. 2012). They found the titania particles calculated at 450 °C can collect
and go through the great pores of the activated carbon substrate, including a very
burly contact among carbon matrix and titania. The contact between them leads to
visible synergy to increase photocatalytic capacity for the degradation of the chro-
motrope 2R. The prepared nanocrystal anatase titania particles install on the activated
carbon at a fewer temperature with the hydrolysis of the titanium but oxide in the
acidic aqueous solution (Andronic et al. 2014). It is noticed that phenol toxin was
absorbed by activated carbon, and after that drifted constantly over titania, which
consequently accelerate photocatalytic oxidation. On the other side, the chemical
vapor deposition method is used for nanosized titania particles that were exposed
to stick to activated carbon, tetra-butyl titania and to offer large activities on the
behalf of the photodecomposition of methylene orange in the water. Adding of water
in titanium tetra-isopropoxide vapors was described to make possible CVD method
at a higher deposition rate and lower temperature. Introduction of H2 O vapors for
the duration of CVD method and adsorption on the activated carbon in prior was
announced to be critical to get hold of anatase-type titania nanoparticles on the acti-
vated carbon surface. Investigations have also clear that the HNO3 treatment results
in more orderly titania loading by CVD, in comparisons with other oxidation treat-
ment. titania: activated carbon has been formed as a result of using dropping the
support in solution produce with the alkoxide hydrolysis as well, and subjected to
heat operation at 300–500 °C. In an alternative process, it can be produced by adding
TiCl4 drop by drop in aqueous suspensions of activated carbon, come after by heat
operation at 500 °C in N2 atmosphere (Tryba et al. 2003). Load the titania powder
exactly over activated carbon that has been achieved as a result of combining titania
in activated carbon aqueous suspension with stirring. On the other side, loading more
activated carbon filter, produced as a result of gluing granular activated carbon over
the glass cloth and it was formed by the water suspension of five mass% titania, and
the conclusion titania: activated carbon particles inside CCl4 solution of pitch, come
after by heat operation at 750 °C. In resultant hybrid system, titania particles over
activated carbon were expected layered with carbon; composed with the pitch at the
stage of the heat operation, it may function to repair titania particle over the activated
carbon surfaces. Titania particles also were being able to load over activated carbon
by spray-desiccation procedure, with a little modification in the pore structure of
the activated carbon (Gao and Liu 2005). In the other study, loading of titania over
the activated carbon surface was taking place via dip-activated carbon particles in a
peroxotitanate solution, and after heating at 180 °C in a Teflon lined stainless-steel
vessel, following by calcinations at 300–800 °C (Slimen et al. 2011). With the help
of the activated carbon particles of 0.16–0.26 mm, the disjunction of the particles
from the solution was not too much harder, and photocatalytic action on behalf of the
decomposition of MO almost remains identical for five cycles. Titania has also been
achieved by plugging the pore of activated carbon by paraffin. After loading titania,
by removing the paraffin at 250 °C in the air, the high surface region of pristine AC, it
could be recuperated as well as the high photocatalytic action was procured basically
for the decay of methylene blue (MB) (Li and Liu 2012). Titania: activated carbon
has also been composed by mixing titania particles with some liquid or solid-state
carbon precursor. By hydrolysis of tetraisopropyl orthotitanate, titania was caused in
the exterior region of the polyvinyl butyral (PVB) and titania overloaded PVB was
carbonized at a high temperature in the flow of CO2 . Titania-loaded carbon micro-
spheres with 25 μm diameter have been prepared from the titania-loaded cellulose
microspheres, composed with one-step stage division using the sodium polyacrylate
aqueous solutions and cellulose xanthate with the isolated titania powder.
Photocatalytic Activities
As a model of titania: activated carbon photocatalytic process can be more of a com-

plex issue, it starts the photo-intensity to the classical aspects of the heterogeneous
catalytic system, e.g., temporal variations in concentration of iminoctadine triacetate
(IT) that is frequently used in excess plus orchard fields like an insecticide, and in the
water path of the fields, it is exposed for pristine activated carbon and three titania:
AC. The hybrid systems were kept without any light on them for 200 h to saturate
IT adsorption and after that showing to ultraviolet irradiation. After 800 h behind
this, the sample was separated from given a test solution and spread once more in
the virgin 1.87 × 10−4 mol/L solution, and again kept without any light in it for
approximately 200 h, and then exposed to ultraviolet radiations. As far as pristine
activated carbon is concerned, concentration of pollutants was initiated to survive
approximately steady without any light and to spread to some extent beneath ultravi-
olet irradiation. The bottom line is that the photocatalysis system of titania: activated
carbon could have the similar photocatalytic results without any light and under
ultraviolet radiations. Before mentioned data was supported by the one who stated
the enhancement of photocatalytic activity for the organic burning of pollutants via
titania: activated carbon enzyme. It is stated that the concentration of 4-chlorophenol
solution demotes rapidly for the titania: activated carbon than titania, saying that
it enhances photo-organic burning approximated by a pseudo-first-order equation
with a linear relationship between time and concentration change. The same harmo-
nious result was noticed in the organic burning of pH and 2, 4-dichlorophenoxyacetic
acid applying similar activated carbon and titania sample. Furthermore, the pH dis-
integration establishes to be dependent upon the mass ratio of titania to activated
carbon (5/10 to 75/10) (Aruldoss et al. 2011). The harmonious result thought to be
attributable to the fast movement of pH molecules at the start adsorbed on the acti-
vated carbon on the outer surface of titania; the motivating force of that movement
is most probably the differentiation in the surface concentration of pH between acti-
vated carbon and titania. Defined proportion of pH was found to remain at AC, even
after the proportion sample becomes negligibly small.
1.3.2.2 Activated Carbon/ZnO Photocatalysis System
ZnO/activated carbon finds broader attraction of use, due to some of the excellent
behaviors of ZnO, such as wider availability, stability, and suitable band gap of
energy. Problems associated with the usage of ZnO alone as photocatalysis material
are as well partitioned; especially, the complexity in unraveling the powder with the
sample after the reaction is over and gathering of particles in delay, particularly at
high loading and complexity in purpose to the consistent flow of the domain system,
has been approved by its surface properties.
The problem is that activated carbon has been declared good as for the sup-
port of the ZnO photocatalysis system. Replying on using of di-oxygen, photo and
entirely mineralized organic as well as inorganic substances and particularly bio-
recalcitrant, make the technique environmentally friendly for toxic waste reduction
schemes. Spherical activated carbon particles having ZnS and ZnO were formed from
a cation-exchange resin (polystyrene with sulfonate groups and cross-linked by di-
vinyl-benzene) and ZnCl2 aqueous solution, followed by carbonization at almost
500–900 °C (Wang et al. 2008). This has been reported that ZnO is an appropriate
substitute to titania for the photodegradation of Acid Red 14, an azo dye, because it
is the photodegradation processes that are being proved to be similar to titania.
1.4 Activated Carbon Photocatalytic Systems: Future

Trend
1.4.1 Granular and Spherical Activated Carbon

Photocatalytic Systems
In all kinds of AC, the spherical activated carbon has benefits, because of their
frictionless surface, high-quality fluidity, and good strength of the powdered and
rough activated carbon. Carrying this forward, many proposals have lately been
examined the sustainability of titania to spherical activated carbon (Yao et al. 2012).
But there are some statements on the granular activated carbon that supported titania
photocatalysis substrate which could enhance the demolishing efficiency of many
organic compounds, regarding many environmentally related conditions.
Granule activated carbon supports titania powdered by adding more pollutants

and alternatives around the titania. The pollutants and alternatives can diffuse to
the surface of titania. Granular activated carbon also reduces titania jelling, which
lessens its surface, thereby reducing its enzymatic activities. This was brought by the
theory that the absorptivity of activated carbon depending strongly on the molecular
morphology and size of the pollutant particles to the titania surface happens straight-
forwardly from the solution, and not through the activated carbon surface. The titania
can destroy the pollutants, leading to again generation of granular activated carbon
in this situation. Most of the porous activated carbon is still in granules, and the
problem of separation and recovering of the photocatalysis system from the reaction
environment is already present.
1.4.2 ACF Photocatalysis System
The surface area characteristics of the ACF are identified to depend powerfully on
the creative processes, affecting the load of titania and eventually the adsorption of
pollutant particles. Nevertheless, the ACF-supported titania photocatalysis substrate
has sometimes been used for the removal of gas-phase pollutants in the environment.
1.4.3 Graphene/Titania Photocatalysis System
A lot of the hard work is used for the combination of titania–graphene photocatalysis
hybrid system (Sin et al. 2011). Due to a higher specified surface region, graphene
appeared like a better help to prepare the overloaded nanoparticle metal oxides to
attain an identical division not including aggregation. Betterment of the photocat-
alytic actions of titania–graphene hybrid is associated with huge two-dimensional
planar graphene structure supporting the dye adsorption plus squeezing electron—
hole rejoining because of higher electrical conduction property has been indicated by
the morphological analysis of titania/graphene photocatalysis system. Absorption of
additional catalyst particles into a particularly graphene leaf at individual places can
supply better dynamically in achieving the choosy catalytic otherwise logical proce-
dures and adjusts the composition also the morphology of photocatalysis materials
to enhance their photocatalytic results.
1.4.4 Titania/CNT Photocatalysis System
Barring graphene, carbon nanotube (CNTs) has been regarded as a more attrac-
tive catalytic support than activated carbon because of combination of electronic,
adsorption, and specific semiconducting characteristics. Studies of titania: CNTs
reveal a considerable synergy effect with the metal oxides and carbon phases (Woan
et al. 2009). Going further, researchers have shown that CNTs can enhance the
adsorption and photocatalytic activity of titania in the presence of ultraviolet. Single-
walled CNTs execute enhanced and selective photocatalytic oxidation of pH. Hetero-
structure CNTs consists of titania-xNx and C prepared by carbonization of electron-
spun poly-acrylonitrile nanofibers containing stabilized titanium oxo-acetate. So
CNTs can be used as a reliable material for environmental pollution clearing and
can be used to improve the photocatalytic efficiency of titania.
1.4.5 Titania: Activated Carbon Semiconductor Doped

Some researches upon doping an additional semiconductor over outer surface of tita-
nia: activated carbon include SnO2 , V2 O5 , ZnO, ZrO2 , and CsS (Liao et al. 2004).
The entire of it confirms the superior photodegradation efficiency as compared to
the titania: AC. Recent researches have reported the modification of titania: acti-
vated carbon by semiconductor doping that has led to the improvement on removal
of specific containments in the gas resulting in the changes of the physical and
chemical properties of the carbon materials. Iron (Fe3 O4 ) dopant titania: activated
carbon has been found as a promoter to photocatalysis with a good performance
on degradation of congo red and methyl orange. Some researchers have combined
the Fe3 O4 compound with titania: activated carbon with aiming at preparing photo-
catalysis substrate with magnetic core and photoactive encapsulation. They proved
that hybrid systems had magnetic properties and could be separated by magnetic
materials. It points out that the magnetic hybrid photocatalysis system can also be
magnetically disturbed by a discontinuous magnetic field in an interrupted system,
but found that the photocatalytic activity of the hybrid system declined because the
magnetic particles experienced the light dissolution (Ao et al. 2008).
1.4.6 Titania: Activated Carbon Nonmetal Doped

Doping of nonmetal, such as N, P, B, C, S, F, chlorine, and bromine, has been

also widely used to improve the photocatalytic or to extend the photo-absorption
into visible light of titania: activated carbon system. Among them, the P-doped tita-
nia: activated carbon has recently attracted increasing interest due to its enhanced
little band gap. It has an adsorption property in the visible light region, and also
found that phosphorous-doped titania: activated carbon prepared by the buffer solu-
tion method with NaH2 PO4 as precursor showed a greater photocatalytic activity of
acetaldehyde organic burning under visible light absence than the pure sample. It
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ogniqualvolta il re vi tornava, e ben pochi s’attaccarono alla fortuna
del nuovo signore. Mentre la nobiltà ribramava l’antica dominazione,
le persone colte stomacavansi d’un assolutismo non palliato dalla
gloria; la plebe rimpiangeva i tempi in cui non pagava nulla; e a
guarnir la città, non tanto contro i forestieri come contro i cittadini,
bisognava tenere più soldati che non ne desse il Genovesato, ed
erigere fortezze minacciose.
Re Vittorio Emanuele, si dicesse pur raggirato dalla moglie, dal
confessore, dal confidente, palesava però intenzioni benevole;
lasciava poc’a poco sottentrare le nuove idee e nuove persone; e
dopo gli odiati Cerutti e Borgarelli, chiamò al ministero il conte
Prospero Balbo, onorato per mente e per liberalità secondo i tempi e
il ceto, che impacciato da tutto l’organamento burocratico, sperò alle
urgenti riforme supplire con palliativi. Secondando la moda, si diè
voce che stava in lavoro una costituzione, e se non veniva agli
effetti, imputavasene l’Austria, la cui vicinanza impacciava
l’indipendenza del regno; l’Austria, potenza preponderante in Italia,
spauracchio universale, su cui i governanti versavano anche le colpe
proprie. Rimedio unico, infallibile a tutti gli abusi acclamavasi la
costituzione: questa al Piemonte attirerebbe l’attenzione e i voti di
chiunque aspira al meglio nazionale, e d’un soffio diroccherebbe
l’Austria, reggentesi solo sul despotismo: gli impazienti
raddoppiavano d’attività nelle combriccole dei Carbonari, degli
Adelfi, de’ Maestri sublimi; e quando scoppiò la rivoluzione di Napoli,
più sorrise il desiderio d’emancipare il Piemonte dalla tutela
austriaca, e metterlo a capo dell’Italia redenta.
Allora le società secrete abbracciarono moltissimi soldati, più
avvocati e professori, e gl’impiegati fin nelle somme magistrature, e
non pochi del clero, e tutti gli studenti; poi propagate nelle provincie
compresero sindaci e parroci, legarono intelligenze colle lombarde e
romagnole. L’antica lealtà savojarda repugnava dalle congiure; l’onor
militare rifuggiva dal calpestare il giuramento di fedeltà; ma si fece
intendere che non trattavasi di ribellarsi al re, bensì di salvarlo dalla
congiura dei preti e dei nobili e dalla servitù, dell’Austria, che si
spargeva volesse obbligare a ricevere guarnigione tedesca, e
concorrere alla spedizione contro di Napoli; anzi, essa pensasse
trarre in un arciduca il Piemonte, a danno di Carlalberto principe di
Savoja Carignano.
Questo giovane rampollo del ramo cadetto reale, educato
popolarmente a Parigi, erasi mescolato d’amicizie, di studj, di
godimenti, d’intelligenze colla gioventù coeva; e poichè de’ quattro
fratelli della Casa regnante nessuno lasciava figliuoli maschi,
trovossi vicino al trono, e fu messo granmastro d’artiglieria. In
quest’arma molti aderivano a’ Carbonari, ed essi gli posero indosso
la febbre di divenire illiberatore d’Italia. Il conte Santorre Santarosa
spingeva a venire ai fatti, mentre sollevata Napoli, incalorite le menti
dalla rivoluzione greca e dalla spagnuola, imbarazzate le Potenze;
Francia commossa parlava di vessillo tricolore, di costituzione del
1791; la Germania, reciso il nervo austriaco, volea rialzare il
liberalismo; Italia esser matura; leverebbesi come un uomo solo per
acquistare la libertà, l’unità, l’indipendenza. Quando poi gli Austriaci
mossero verso Napoli, certo (diceasi) gli eroi popolari terranno testa
lungamente (1821); i monti sono le barriere della libertà, nè i briganti
furono mai domabili: intanto l’insurrezione in Piemonte si compirà
senza ostacoli, Milano seconderà, Romagna e i piccoli Stati non
tarderanno, e tutta l’Italia superiore si troverà costituita prima che
gl’Imperiali tornino a reprimerla; Francia, se anche non favorisse,
non permetterà mai che l’Austria entri armata in paese che confina
con essa.
Si cominciò al solito dalla stampa clandestina, e girò un reclamo, in
cui pretendeasi strappare al re la benda postagli da’ suoi cortigiani,
rivelandogli esausto l’erario, il denaro stillato dalla fronte del popolo
è prodigato a impinguare le più alte e inutili persone dello Stato; gli
uomini a cui è affidata l’economia pubblica sagrificano all’egoismo
personale gl’interessi della patria. — Maestà, se invece di cumulare i
poteri in una classe sola, aveste chiamato il consiglio di tutta la
nazione, i lumi generali avrebbero riparato a questi mali, nè voi
avreste il rimorso d’aver condotto a rovina lo Stato. Il vostro Governo
avversò sempre la dottrina; l’istruzione primaria è abbandonata
all’ignoranza e all’impotenza dei Comuni; l’educazione media è
tiranneggiata dai Gesuiti; gli studj filosofici involti nella ruggine
monacale; i legali, disordinati per mancanza di legislazione;
l’Università condotta da uomini o inetti o stupidi o maligni, gl’ingegni
migliori vanno a cercare un pane altrove, o vivono sprezzati. I favoriti
hanno il monopolio dei diritti e dei privilegi, pesando sulla classe
industriosa della società. Le provincie dai governatori delle divisioni
sono rette come paese di nemici. Le amministrazioni civiche e
comunali cascano in disordine per l’indolenza, l’incapacità, la
discordia dei capi. La religione, in mano dei Gesuiti, è strumento
d’ambiziose voglie e di tenebrosi raggiri. La legislazione civile ha
l’arbitrio per base, la criminale il carnefice per sostegno. Uno strano
ed informe accozzamento di leggi romane, di statuti locali, di
costituzioni patrie, di editti regj, di sentenze senatorie, di
consuetudini municipali, hanno tolto la bilancia alla giustizia, e
lasciata la strada al despotismo dei tribuni. L’esercito non ha forza
morale, perchè composto di elementi contrarj, di corpi privilegiati, di
brigate varie tra loro di dottrine, di lingua, di diritti, comandati da capi
promossi non per merito ma per favore. Dei militari una parte è
avvilita, perchè si vede preclusa la strada ai gradi maggiori; tutti
indignati ai maneggi del vostro Governo, il quale medita di trafficare
la loro vita col gabinetto d’Austria. No: il nome de’ soldati piemontesi
non si confonderà mai col tedesco; essi sono e saranno italiani».
L’11 gennajo 1821 alquanti studenti dell’Università comparvero al
teatro d’Angennes con berretti rossi alla greca. Arrestati, in onta del
privilegio che li sottoponeva al magistrato degli studj, furono messi in
fortezza: i condiscepoli irritati si asserragliano nell’Università, a gran
voce domandando la scarcerazione de’ colleghi: il reggimento
Guardie mandato a calmarli trova resistenza, e fa sangue. Tali
manifestazioni sogliono chiamarci primizie di martiri; e ne rimase una
cupa irritazione. Se n’incaloriva la faccenda delle società secrete;
ma quale costituzione adottare? la francese, la spagnuola, o
l’inglese? perocchè sempre si stava all’imitare, anzichè fondarsi sulle
basi storiche e nazionali. Per risolvere si mandano tre deputati alla
vendita suprema di Parigi, alla quale faceano centro i Liberali di
Spagna, i Radicali d’Inghilterra, gli Eterj di Grecia, i nostri Carbonari;
e vien data la preferenza alla costituzione spagnuola, come scevra
d’elementi aristocratici e tutta popolare. Ma il Governo, istruitone
forse dalla Polizia francese, intercettate le lettere del principe La
Cisterna e del marchese Priero, conobbe partecipi gl’impiegati e i
militari, cioè quelli che doveano opporsi, onde non sapeva o non
poteva impedire. Il conte Moffa di Lisio e il marchese Sanmarzano,
uffiziali sospetti, invitati a partire da Torino, ricusano, e con Giacinto
Collegno, ajutante di Carlalberto, con Santarosa, Morozzo, Ansaldi,
Bianco, Baronis, Asinari ed altri uffiziali prendono concerto di
rivoltare l’esercito, sorprendere Alessandria, acclamare Vittorio re
costituzionale dell’alta Italia.
I cospiratori non si erano intesi co’ Napoletani, onde non fu nè
contemporaneo il sollevarsi, nè uniforme l’intento; poi i preparativi
erano impacciati dal tentennare del principe di Carignano fra la gloria
e la fedeltà. Ma la rivolta scoppia fra i militari a Fossano ed
Alessandria (9 marzo), costituendo una giunta della Federazione
italiana; fra il restante esercito corre il grido d’Italia, di francare
dall’Austria il re, sicchè possa seguire i moti del suo cuore italiano, di
porre il popolo nell’onesta libertà di manifestare i proprj voti al trono,
come i figli a un padre; e scritto sui vessilli, Regno d’Italia,
Indipendenza italiana; e gridando, Viva la costituzione, Morte agli
Alemanni, i sollevati s’accostano a Torino. Quivi gli studenti e
alquanti militari col capitano Ferrero attruppatisi a San Salvario, che
allora giaceva un pezzo fuor di città, gridano la costituzione; altri
uccidono il colonnello Raimondi che li richiama al dovere; ma non
secondati dal popolo, con disastrosa marcia sfilano come vinti verso
Alessandria, il cui comandante fu ucciso [184].
Il re non osa ricorrere alla forza, ma espone lealmente la
dichiarazione fatta dai re a Troppau contro ogni novità, mostrando
come ne resterebbe pericolata l’indipendenza; e non volendo nè
promettere quel che non è disposto a mantenere, nè autorizzare atti
che agli stranieri diano pretesto d’invadere il suo paese, depone una
corona (13 marzo) ch’egli non potea conservare se non colla guerra
civile.
Il Carignano, da lui nominato reggente, esitava a palesare le sue
intenzioni, sicchè schiamazzi, poi armi. Dalla cittadella sorpresa
gl’insorgenti minacciano far fuoco sulla città: molti soldati lasciano le
bandiere, considerandosi come sciolti dal giuramento dato al re;
l’anarchia sottentra; quando il Carignano proclama la costituzione
spagnuola, gli applausi vanno al cielo, e al nome di Carlalberto si
accoppia quello di re d’Italia.
In Lombardia avea preso piede la setta della Federazione italiana, e
da un pezzo tramava nelle sale del marchese Gattinara di
Breme [185] e del conte Federico Confalonieri, mascherata sotto il
velo d’imprese benefiche o progressive, come una distilleria d’aceto
a Lezzeno, un battello a vapore sul lago di Pusiano e sul Po,
l’illuminazione a gas, il mutuo insegnamento, un bazar, il giornale del
Conciliatore, apostolo del romanticismo. L’Austria, avutone fumo,
arrestò Silvio Pellico, giovane saluzzese educatore in casa Porro, la
cui Francesca da Rimini avea fatto sperare all’Italia un secondo
Alfieri. Allo scoppiar della rivoluzione piemontese si rinserrarono le
file in mano del conte Confalonieri, principale nella sciagurata
insurrezione del 1814, poi nei suoi viaggi legatosi co’ primarj liberali,
e che si mise attorno Demester e Arese antichi uffiziali napoleonici,
Giuseppe Pecchio economista, Pietro Borsieri letterato, i marchesi
Giorgio Parravicini e Arconati, Benigno Bossi, i fratelli Ugoni di
Brescia, il cavaliere Pisani di Pavia, il conte Giovanni Arrivabene di
Mantova, l’avvocato Vismara novarese, Castiglia, altri ed altri. Essi
aveano già disposta sulla carta una guardia nazionale, una giunta di
Governo; neppur l’inno mancava, opera d’un sommo poeta; e
appena l’esercito piemontese varcasse il Ticino, insorgerebbero
Milano, Brescia, le valli, le campagne, occupando le casse e le
fortezze di Peschiera e Rôcca d’Anfo.
I Lombardi spedirono al Sanmarzano, generale degli insorgenti
piemontesi, con numerose firme esortandolo a venire. — Cominciate
ad insorgere voi», ci diceano i ministri piemontesi; e noi
rispondevamo: — Da soli non bastiamo a vincere; ma senza noi, voi
non bastate a difendervi». Il vero è che Sanmarzano contava
appena ducento dragoni e trecento fanti; ma poichè coll’audacia
dominansi le rivoluzioni, risolvea ritentar l’impresa, massime che gli
Austriaci, collo sgomento di chi accampa in terra nemica, aveano
ritirato ogni truppa dal Ticino, e il vicerè lasciavasi vedere a incassar
mobili e vendere vasellame. Ma il ministro piemontese Villamarina
disapprovò quella temerità; e il reggente che, come dice il Santarosa
«voleva e non voleva», mandò quel reggimento ad Alessandria. Così
la rapidità degli avvenimenti, la inconcepibile mancanza di concerti,
la titubanza dei capi, la paura che Torino cessasse d’essere capitale
del Regno, elisero il moto della Lombardia, donde sol pochi giovani
corsero in Piemonte ad aggregarsi al battaglione di Minerva.
Binder ambasciatore austriaco, insultato fin nel suo palazzo, parte
lasciando una nota minacciosa. Il duca del Genevese che, per la
rinunzia del fratello, diventava re col nome di Carlo Felice, da
Modena dichiara ribellione ogni attenuamento della piena autorità
reale, e punibile chi non torni all’ubbidienza; ed ordina le truppe si
concentrino a Novara sotto il generale La Torre. Carlalberto, anche
dopo giurata la costituzione, non si era risoluto a convocare i collegi
elettorali, bandir guerra all’Austria, entrare in Lombardia. Udita poi la
dichiarazione del nuovo re, e che questo avea invocato l’Austria,
dicendo minacciata la propria vita, e sè incapace di padroneggiare la
rivoluzione, fugge all’esercito regio a Novara, e di là pubblica che
«altro ambir non saprebbe che di mostrarsi il primo sulla strada
dell’onore, e dar così l’esempio della più rispettosa obbedienza ai
sovrani voleri».
Era il 23 marzo, il giorno stesso d’un altro proclama ventisette anni
dopo.
Quella fuga toglieva agl’insorgenti ogni apparenza di legalità: ma
risoluti di non cedere, creano una giunta provvisoria [186]; sparigliano
proclami e bugie. Intanto ogni cosa va sossopra; la Savoja si
chiarisce pel re; la brigata che porta quel nome, ricusa disertare,
onde fu dovuta rimandare in patria; i carabinieri in arme si recano
all’esercito regio; a Genova il governatore Des Geneys, che
annunziò la defezione di Carlalberto, è assalito, trascinato per le vie,
e a fatica salvato dai generosi che non voleano contaminare con
violenze la rivoluzione; i Liberali medesimi discordano, quali
caldeggiando la Camera unica, quali la duplice, quali unitarj, quali
federalisti. Santarosa, fatto ministro della guerra, cerca destare il
coraggio colle speranze, e collo spargere che gli Austriaci furono
disfatti dai Napoletani, e le valli Bresciane insorsero furibonde; ma
ecco giungere certezza della disfatta degli Abruzzi, e che centomila
Russi sono in mancia; poi addosso ai Liberali muovono i Realisti col
generale La Torre e gli Austriaci col generale Bubna (9 aprile), che in
Lombardia aveva, se non alle trame, partecipato alle speranze de’
Carbonari; presso Novara succede un’affrontata, e la rivoluzione
piemontese è finita.
Carlalberto ricoveratosi a Milano, è dal generale austriaco
beffardamente presentato come re d’Italia: Carlo Felice a Modena lo
tratta come uno scapato, e la lettera di lui getta in viso al suo
scudiere: egli si ritira a Firenze a digerire l’obbrobrio, confessare i
suoi torti e farne scusa, solo appoggiato dall’ambasciatore francese
per rispetto alla legittimità [187].
La società de’ Maestri Sublimi, raffinamento della Massoneria, e che
professava il regicidio, fu dalla Francia trapiantata a Ginevra dal
fiorentino Michelangelo Buonarroti, antico adepto di Babœuf, che
v’istituì un congresso italiano per diffonderne i dogmi nel nostro
paese. Alessandro Adryane, che n’era diacono straordinario, fu
spedito qui per rannodare le rotte fila; ma a Milano lasciossi cogliere
con tutte le carte, le quali diedero a conoscere la trama, senza
bisogno che la rivelasse Carlalberto, come si ciancia. Da nove mesi
era finito il parapiglia di Piemonte quando si cominciarono i processi
contro i Lombardi, parte a Milano, parte a Venezia [188], da una
commissione speciale, alla cui testa il tirolese Salvotti. In quelli
l’imputato si trovava all’arbitrio d’un giudice, senza difensori,
senz’avere sott’occhio le sue e le altrui deposizioni; durava interi
mesi di solitudine nel carcere fra un esame e l’altro; e qualche volta
l’inquirente, fattosi mansueto, gli diceva: — Ecco, ella è interamente
nelle mie mani. Qui non siamo in paese di pubblicità
compromettente. Confessa ella quel che del resto noi sappiamo?
l’imperatore le fa grazia, ella torna a casa sua onorato. Persiste al
niego? sta in me il diffamarla, e spargere che ha tutto rinvesciato,
che tradì i compagni, e così torle quel ch’ella mostra valutare tanto,
la pubblica opinione».
Ad arti di simil genere, piuttosto che a torture fisiche, non tutti
resistettero; vi fu uno che, per generosità di salvare un amico, corse
a denunciare se stesso, poi accortosi dell’errore si finse pazzo, e per
mesi sostenne la straziante simulazione; altri credette scagionarsi
col provare che aveva dissuaso i Piemontesi dall’invadere la
Lombardia; altri ammise di quelle tenui concessioni che conducono
ad altre; tanto che si potè raccogliere onde condannare
Confalonieri [189], Adryane, Castiglia, Parravicini, Tonelli, Borsieri,
Arese e molt’altri a Milano, dove furono esposti sulla gogna il 24
gennajo 1824. E già a Venezia, la vigilia di Natale, giorno di
gratulazioni e feste ecclesiastiche e civili, erasi letta la sentenza di
Pellico, Maroncelli, Solera, Villa, Oroboni, Foresti, Fortini ed altri e,
cosa insolita in quella stagione, l’accompagnarono tuoni e ruggito del
mare sotto un insistente scirocco, onde al domani la città fu invasa
dall’acqua, e tutto il litorale ne patì fin alla Spezia e a Genova.
Furono portati allo Spielberg, ove alcuni soccombettero, quali il
conte Oroboni, il veterano Morelli, il Villa; Maroncelli perdette una
gamba; altri poterono dopo molti anni uscire ancora a narrare i proprj
patimenti [190]. E mentre alcuni li esagerarono, o posero in evidenza
se stessi, o denigrarono altrui, Silvio Pellico li raccontò senza
rancori, senz’arte; e tutto il mondo lesse le sue Prigioni, e la pietà
per quei sofferenti partorì esecrazione a colui che così facea soffrire:
e che pure non avea mai lasciato che l’applicazione dell’estremo
supplizio gli togliesse di esercitare il diritto più prezioso pei re, il
ripiego più nobile pell’uomo, la grazia e la riparazione.
Gioja, Romagnosi, Trechi, Mompiani, Visconti e altri fur on rilasciati
senza condanna [191]. I quali poi restavano in condizione tristissima,
chè, mentre la Polizia perseverava nell’adocchiarli e vessarli, quasi a
giustificarsi dell’averli perseguitati, il pubblico (troppo solito complice
degli oppressori) dubitava di loro perchè non condannati, e
accogliendo le sinistre insinuazioni sparse d’alto luogo, finiva per
temere e odiare quelli ch’erano temuti e odiati dal Governo.
In Piemonte si fecero 92 sentenze di morte, 432 di lunga o perpetua
prigionia [192], ma tutti in contumacia, essendosi lasciato partire chi
volle; il notajo Garelli e il sottotenente Laneri furono messi a morte, e
in effigie La Cisterna, Caraglio, Collegno, Lisio, Morozzo, Regis,
Santarosa; di seicennovantaquattro uffiziali inquisiti, dugenventi
furono destituiti, e così molti impiegati civili.
Anche negli Stati Pontifizj i cospiratori abbondavano: e il Puccini,
direttore della Polizia toscana, scriveva al Corsini plenipotenziario al
congresso di Lubiana: «Nelle Marche e nelle Legazioni sono assai
numerose le sêtte, e grandi mezzi adoprano per diffondere l’odio
contro i Governi monarchici, e sperano nei torbidi d’Italia, comunque
arrivino. L’odio di questi partiti si sfoga colle maniere dei tempi del
duca Valentino. Molte uccisioni vennero commesse negli anni scorsi
sopra ecclesiastici ed impiegati pubblici a Forlì, Ravenna, Faenza;
altre in maggior numero modernamente, certo per odio di parte».
Istantemente aveano chiesto che le truppe sarde si avvicinassero al
confine, ma non ne fu nulla; e quel Governo, ripigliata forza,
cominciò gli arresti; di quattrocento processati, molti, principalmente
per opera del Rusconi legato di Ravenna e del Sanseverino di Forlì,
condannò alla pena capitale, che il papa commutò nella reclusione. Il
granduca non credette necessarj i processi perchè non ebbe paura.
Maria Luigia li lasciò fare, e vi furono involti Ferdinando Maestri e
Jacopo Sanvitali professori; ma commutò le pene in esiglio. A
Modena nel 1817 erasi formata una società della Spilla nera per
rassicurare i Napoleonidi: e al tempo stesso i Massoni, gli Adelfi, le
Chiese dei sublimi maestri perfetti aveano adepti, e s’erano ascritti i
dottori Carlo e Giuseppe Fattori di Reggio, nella cui casa teneansi le
adunanze, il capitano Farioli di Guida, il dottore Pirondi, Prospero
Rezzio e molti ebrei [193]. Tutte le Società aveano statuti proprj, ed
alcune v’univano l’obbligo di farsi vicendevoli correzioni e di non
vagheggiare la moglie dell’amico: comune era quello di uccidere chi
fosse condannato o avesse rivelato il segreto: pagare una certa
somma, manifestare a tutta la società le operazioni del Governo.
Sconfitti su tutti i punti, i Liberali rifuggono in Ispagna a fiancheggiare
una causa che sentiano dover soccombere, ma che era la loro; e a
mostrare, colle generose morti, che non erano colpevoli delle fughe
di Rieti e di Novara. Altri crociaronsi in ajuto della Grecia, dove a
Sfacteria perì il Santarosa, eroe all’antica.
Gli alleati, all’udire l’inaspettato successo, esclamano «doverlo
attribuire non tanto ad uomini che mal comparvero nel giorno della
battaglia, quanto al terrore onde la Provvidenza colpì le ree
coscienze»; e protestando di lor giustizia e disinteresse, annunziano
all’Europa d’aver occupato il Piemonte e Napoli, e nella lora unione
«una sicurezza contro i tentativi de’ perturbatori». Insieme
partecipano ai loro ministri presso le Corti «essere principio e fine di
loro politica il conservare ciò che fu legalmente costituito, contro una
setta che pretende ridurre tutto a una chimerica eguaglianza»;
annunziano altamente che «i cambiamenti utili o necessarj nelle
leggi o nella amministrazione degli Stati, non devono emanare che
dalla libera volontà di quelli che Dio rese responsali del potere [194].
Così essi erigonsi custodi e dispensieri unici della verità, della
giustizia, delle franchigie: e i Liberali ebbero servito agl’interessi
dell’Austria, dandole occasione di estendere l’alta vigilanza e quasi
l’impero su tutta la penisola, da lei sottratta ai tumulti o al progresso.
Poi a Verona (1822) s’adunarono a congresso i re di tutta Europa
colla grandezza loro e cogli avanzi di loro miserie: e i diplomatici più
vantati dichiararono che «resistere alla rivoluzione, prevenire i
disordini, i delitti, le calamità, assodar l’ordine o la pace, dare ai
Governi legittimi gli ajuti che aveano diritto di chiedere, fu l’unico
oggetto degli sforzi dei sovrani; ottenutolo, ritirano i soccorsi che la
sola necessità avea potuto provocare e giustificare, felici di lasciare
ai principi il vegliare alla sicurezza e tranquillità del popolo: e di
togliere al mal talento fin l’ultimo pretesto di cui possa valersi per
ispargere dubbj sull’indipendenza dei sovrani d’Italia». In fatto
l’Austria si persuase a sgombrare il Piemonte e abbreviare
l’occupazione del Napoletano; della Grecia non si ascoltarono
tampoco i deputati, benchè il papa gli avesse accolti ad Ancona e
raccomandati; si convenne dei casi in cui i re si dovrebbero sussidj
reciproci; si stabilì soffocare la rivoluzione anche in Ispagna, e
l’incarico ne fu commesso all’esercito francese, che tra le grida di
Muoja la costituzione, Viva il re assoluto, procedette senza ostacolo
fino a Siviglia. Carlalberto, combattendo al Trocadero, aveva in
faccia ai re lavato la macchia dell’essersi lasciato salutare re
d’Italia [195].
La facile caduta di rivolte militari o di popolari sommosse, fecero
persuasi i re d’essere sicuri, e che niuna reale efficacia possedesse
lo spirito liberale, che amavano confondere col rivoluzionario;
bastasse affrontarlo per vincerlo; e pesarono sull’Italia con una
taciturna oppressione non ricreata da verun lampo di speranza.
CAPITOLO CLXXXIV.
La media Italia. Rivoluzioni del 1830.
Nei Liberali questo momentaneo agitarsi sotto le bajonette de’

padroni lasciò scontentezza, ma non sconforto: e poichè, invece di
studiar le vere cause della ruina, la spiegavano colla plateale
ragione del tradimento, altra lezione non se ne traeva se non
d’esecrare i traditori, e non isperare nei principi.
Tanti profughi ond’erano piene non solo Francia, Inghilterra e
Svizzera, ma Barberia e Turchia, rodendo il pane dell’esiglio
rinnovavano que’ tempi del medioevo quando le trame dei fuorusciti
decideano le sorti della patria, e co’ loro scritti mantenevano
l’irrequietudine, eccitando sdegni che pareano speranze. Giuseppe
Pecchio descrisse i proprj viaggi e la vita di Foscolo e la storia
dell’amministrazione finanziera del regno d’Italia e quella
dell’economia politica nel nostro paese, adulandoci: Giovanni
Arrivabene applicavasi all’economia e alla beneficenza pubblica:
Camillo Ugoni continuava la critica letteraria, come il Salò:
Santarosa ed altri raccontavano la rivoluzione di Piemonte, mentre
Pepe e Carascosa duellavano su quella di Napoli: il capitano Bianco
insegnava la guerra per bande: Giannone ordiva un poema l’Esule: il
conte Alerino Palma sedeva nell’areopago della risorta Grecia, e in
quella lingua scriveva delle viti e del vino: le romanze di Giovanni
Berchet milanese rendevano popolare l’esecrazione contro l’Austria
e contro Carlalberto. I libri che si faceano leggere, erano proscritti o
di proscritto; le opere statistiche del Gioja, le giuridiche del
Romagnosi, le mediche del Rasori, le filologiche del Giordani e del
Foscolo, le storiche del Troya, del Colletta, del Sismondi, le poetiche
del Pellico e del Rossetti, le filosofiche del Borelli, prediligeansi
perchè d’autori perseguitati; voleano vedersi allusioni e condanne
contro l’autorità che le proibiva, e il divieto aguzzava le voglie, e
toglieva il criterio di sceverare il vero dal falso. Così crebbe la
smania del leggere e scrivere, del ragionare e ragionacchiare di
politica e d’economia; e si moltiplicarono i giornali.
Era anche questa un’imitazione di Francia, dove i Carbonari, non
avendo potuto insorgere nel 1821, si erano diretti a preparare
l’opinione sia alla tribuna, sia colle gazzette, lanciandosi in una
politica avventurosa, com’è sempre quella che non ha il riscontro
della realtà, ed esercitando quell’opposizione negativa, ch’è
facilissima perchè ha bisogno solo di collocarsi in un punto di vista
differente da quello del Governo, ed è insufflata dalle passioni
invidiose e malevole. Di là quei giornali arrivavano in Italia: i Governi
che ne capivano la potenza a segno di proibirli, non riuscivano ad
opporvene alcuno, il quale alla savia moderazione che concilia
anzichè irritare unisse la prudente franchezza che fa rispettare la
ragione anche quando contraria, e all’elogio dà valore e dignità col
saper disapprovare. Intanto sui Francesi formavasi quel poco di
spirito pubblico, creando bisogni e affetti che non erano i nostri;
lodando una beneficenza che storpia l’uomo per avere il vanto di
dargli le stampelle; erudendosi a una storia tessuta con luoghi
comuni e paradossi; allucinandosi ad un liberalismo che abbaja
contro ciò che s’ha a distruggere, non ragiona sopra ciò che bisogna
sostituire, e vagheggia una democrazia che sconoscendo le parti più
vitali delle nazioni e degli individui, condanna ad abdicare ogni
valore proprio ed inabissarsi nella così detta opinione pubblica, cioè
volgare.
Quest’indeclinabile imitazione de’ Francesi, della loro scienza
incompleta, della filosofia eclettica, della letteratura improvvisata,
della politica rischiosa fu sempre una delle più funeste endemie
degl’Italiani. Intanto i principi nostri credevano che i mali si
rimediassero col negarli, e se la compressione materiale ristabilì
l’ordine esterno, non si provvide all’interna agitazione, cresciuta anzi
ne’ paesi dove non s’era dianzi sfogata, e dei quali or ci avanza a
parlare.
Il papa era stato rintegrato ne’ suoi possessi, eccetto Avignone e il
contado Venesino che Francia si tenne, e le fortezze di Comacchio e
Ferrara a cavallo del Po, volute dall’Austria ad onta delle proteste
pontifizie.
Roma aveva esultato nel ricuperare il Laocoonte, l’Apollo, la Corte,
le solennità, l’aurifera affluenza dei forestieri. Pio VII, tornando
ingloriato dal martirio, non ricercò alcuno per l’operato durante il
Governo francese o nell’invasione di Murat; anzi il generale
austriaco Stefanini, col fare qualche persecuzione, scemò la
propensione che non piccola v’era per gli Austriaci. Col consiglio del
cardinale Consalvi e del Bartolucci, il papa con motuproprio (1816 6
luglio) sistemò l’amministrazione pubblica in aspetto di legge
generale che tenesse dell’antico senza ripudiare tutto il nuovo,
tenendo all’unità e uniformità collo sbandire quelle amministrazioni
molteplici, e ridurre a un centro le giurisdizioni. Lo Stato fu diviso in
diciannove provincie, oltre la metropoli colla comarca; ogni
delegazione in distretti ch’erano quarantaquattro: questi in
seicenventisei Comuni sotto delegati prelatizj. Le Comunità
regolavansi da un consiglio che deliberava, da una magistratura che
amministrava, scegliendone i membri fra il clero, i possessori, i
letterati, i negozianti, salva la conferma del delegato. Roma ebbe un
senatore e conservatori; e così Bologna.
Ai fidecommessi poteasi rinunziare: abolite le servitù e le riserve;
abolite le giurisdizioni baronali, eccetto quelle del cardinale decano
in Ostia e Velletri, e del maggiordomo papale in Castelgandolfo;
aboliti gli statuti municipali, se non in quanto concerne l’agricoltura.
Si sistemò l’imposta, alleggerendola d’un quarto, e doveasi erigere il
rendiconto annuo, compilare un catasto regolare, un registro di tutto
il debito pubblico fruttante il cinque per cento, con una cassa di
redenzione.
Abolito il codice civile e il criminale francese, le commissioni, i giudizj
privati, si accentravano le giurisdizioni, determinando i tribunali
collegiali e le loro gradazioni, con appelli a Bologna, Macerata e
Roma, e una cassazione detta Segnatura; le cause trattate in
italiano, motivate le sentenze criminali, difeso il reo e confrontato coi
testimonj, abolita ogni guisa di tortura; indipendente l’autorità
giudiziale, responsali i magistrati. Ma regolamenti soggiunti
smentirono i preamboli, nè i codici promessi comparvero mai: i fôri
vescovili impacciavano col trarre a sè ogni lite ove fosse implicato un
ecclesiastico: rinacquero i vecchi tribunali della fabbrica di San
Pietro che conosce di qualunque eredità a suffragio delle anime, e
della congregazione de’ chierici di camera per le cause demaniali: la
Segnatura non giudicava definitivamente, ma rimetteva alla sacra
Rota, la quale cogli opinamenti (del resto opportuni a raggiungere la
verità) poteva eternare le cause, ripetendo l’audiatur invece dello
exequatur.
Alla francese continuarono l’ordinamento delle finanze, le ipoteche, il
bollo, il registro: ma il commercio era incagliato da privative e
protezioni; arbitraria la Polizia, diretta dal governatore di Roma, e
che applicava fino la pena del cavalletto. I soldati raccoglievansi per
ingaggio: privilegio dei chierici la istruzione e la censura, come a soli
prelati la diplomazia, e le supreme magistrature amministrative e
giuridiche, e fino il governo delle armi. Il papa ripristinò le accademie
della Religione cattolica, d’Archeologia, di San Luca; malgrado le
indomabili paure dei re, concesse ospitalità alla famiglia Buonaparte;
rielesse cardinali; colle antiche cerimonie canonizzò molti santi, fra
cui gl’italiani Andrea da Peschiera, Costante da Fabiano, Antonio da
San Germano vercellese, Ranieri da San Sepolcro, Francesco
Caracciolo, e le beate Angela da Desenzano, Caterina da Racconigi,
Giacinta Marescotti, Bartolomea Bagnesi fiorentina.
Alla basilica di San Paolo, fondata da Costantino, arricchita
dagl’imperatori e dai pontefici con quadri, musaici, porte di bronzo,
cimelj, marmi, s’apprese il fuoco accidentalmente, e que’ tesori
d’arte e di devozione e ventiquattro colonne di marmo frigio ne
rimasero distrutte. Parve preludere alla fine del pontefice, il quale
allora appunto cascando in camera, si ruppe l’osso del femore, e
soccombette (1823 20 luglio). Eroe da che la prigionia pose fine alle
sue debolezze, nè gradi nè ricchezze attribuì ai parenti; non
commise crudeltà, ma non impedì le malversazioni; e inetto al
governo, abbandonava il paese più povero, disordinato e bollente di
ire. Gli fu dato successore Annibale Della Genga (28 7bre), col nome
di Leone XII; il quale congedò il Consalvi, che lascerà buon nome fra
i ministri di Stato per lo spirito conciliativo ed opportuna fermezza, e
che poco dopo morendo, i molti donativi diplomatici destinò ad
erigere una statua al pontefice, di cui era stato sostegno.
Leone XII, reputato per moralità non meno che per l’accorgimento
politico mostrato come nunzio in Francia, proseguì le cure pastorali
contro «l’irruente empietà, e contro la meticolosa politica, invasata
dalla paura dei forti ed affettante alterigia coi deboli»; comprò la ricca
biblioteca artistica del Cicognara, che l’imperator d’Austria avea
ricusata; fece da giureconsulti esaminare il motuproprio del suo
predecessore; nominò anche una congregazione di Stato, ma subito
la risolse in mera assemblea consultiva. Parve anzi condiscendere ai
retrivi col lasciar vivere gli arbitrj di ciascun dicastero: vennero estesi
i diritti delle comunità; ma se ne’ consigli entravano tutte le classi,
rimaneva separata la nobiltà, con le primogeniture e fedecommessi,
credendo «influisca al decoro del principato»: volevasi anche
ripristinare le giurisdizioni baronali «come l’unico mezzo di ridonare il
lustro alla nobiltà romana», se il concistoro non si fosse opposto. Le
femmine dotate furono escluse dalla successione; rimessi i giudizj a
singoli, invece de’ collegi; aboliti i tribunali di distretto; introdotto di
nuovo il latino ne’ giudizj, e nelle più grandi Università e nelle cinque
minori; ad ecclesiastici affidato il condurre anche il processo dei laici;
attribuito ai Gesuiti il collegio romano, il museo, e l’osservatorio, con
dodicimila scudi di rendita sul tesoro pontifizio; ripristinato il
Sant’Uffizio; estesi i privilegi della manomorta.
Forza era dunque dar torto al papa di prima o al presente, e
facilmente si dava torto ad entrambi, cioè si perdea la fede
nell’autorità. Commissioni di preti ed uffiziali sgomentarono le
Legazioni, solcate da società segrete, che manifestavansi ad ora ad
ora con assassinj di pretesto politico, e contro avversarj che
denunciavansi per Sanfedisti: e un tentativo d’insurrezione nel 1825
in occasione del giubileo, costò la testa a un Targhini. Il cardinale
Rivarola nella legazione di Ravenna in una sola volta, udito il parere
de’ giudici, condannò (1825) cinquecentotto persone; poi ad un tratto
perdonò a tutte, assegnò pensioni ai loro parenti, e cercò
rappattumare Sanfedisti e Carbonari per via di matrimonj, che
riuscirono come Dio vel dica. Essendosi poi attentato alla vita del
legato, egli istituì una commissione severissima, moltiplicò le spie,
lasciò andare alla forca sette omicidi (1828), che il pubblico
compassionò come vittime politiche. Del resto, allorchè si promise
perdono a chi spontaneo venisse a far dichiarazioni, a centinaja vi
accorsero. Tali erano i governati, tali i governanti.
Leone XII aveva divisato di riformare le regole ed il vestire dei frati,
riducendoli a tre soli Ordini: uno di regolari, poveri, di scienza
discreta e gran cuore, che servissero al popolo sussidiando i parroci
e prestandosi agli spedali. Il secondo, tutto all’educazione e
istruzione della gioventù, e a sostenere gl’interessi della religione e
del buon costume. Il terzo di contemplativi, che salmeggiassero,
predicassero, e cercassero l’evangelica perfezione.
Non mancavano i Barbareschi di molestare le coste; ma peggior
vitupero allo Stato Pontifizio veniva dai briganti. L’antico paese dei
Volsci, fra gli Appennini, le paludi Pontine e i monti d’Albano e
Tuscolo, fino al 1809 appartenne alla famiglia Colonna, che all’armi
addestrava quelle popolazioni per ajutarsene nelle sue emulazioni
cogli Orsini e coi papi. E i papi non vi poteano nulla; se non che, alle
persone probe dando un brevetto di cherico, le sottraevano alla
giurisdizione territoriale. I Francesi abbatterono questa feudalità; ma
gli eccessi della coscrizione del 1813 tornarono in armi la
popolazione, e bande di politici vi si formarono in opposizione di re
Gioachino. Sotto il debole Governo sottentrato crebbero di baldanza:
obbedienti a capi quali De Cesaris e Gasparone nelle provincie
romane, Furia e Vandarelli nelle napoletane confinanti, e carichi
d’armi e di reliquie, a torme fin di cento scorrazzavano la campagna
spopolata, e rendeano pericolosissimo il tragitto da Roma al
Napoletano; assalirono e taglieggiarono un collegio alle porte di
Terracina, i Camaldolesi presso Tuscolo; molte famiglie ridussero sul
lastrico; guastarono i commerci, l’agricoltura, la pastorizia. Chi
avrebbe osato negare ricovero e vitto a questi formidabili? Assai
volte il Governo dovette scendere a patto con essi, pure beato
quando qualcuno tornasse a penitenza, e venisse a sospendere a
una Madonna il coltello insanguinato. Il Consalvi, fisso di sterminarli,
s’accontò col Governo napoletano acciocchè non li ricoverasse nel
suo territorio, arse le capanne e i villaggi ove annidavano, e potè
consacrare una festa a commemorazione d’averli distrutti. Ma non lo
erano così, che molto non restasse a fare. Leone XII spedì il
cardinale Pallotti legato a latere con un editto, ove, cessata ogni
misericordia o transazione, intimavasi morte immediata ai briganti
côlti; pena cinquecento scudi ai Comuni ove succedesse un loro
latroneccio. Di fatto si trovarono ridotti aventi, che a Sonnino
capitolarono: ed essi furono mandati nelle fortezze, il paese distrutto.
Lo Stato romano si estendeva fra il 41 e il 45º parallelo per
centrentadue miglia da Ancona a Civitavecchia e ducenquaranta dal
Po a Terracina, con due milioni e settecensettantaduemila abitanti, e
con fama di sterilità a terreni calcari e vulcanici, che sarebbero
ubertosissimi. Il pendìo dell’Appennino che scende al Mediterreneo
presenta vaste pianure, esercitate colla coltivazione grande; verso
l’Adriatico le varietà della piccola trovansi nelle Legazioni, nelle
Marche, nelle valli dell’Appennino. Le Legazioni partecipano della
fertilità della Lombardia; e una popolazione intelligente e laboriosa
prospera la coltura della seta, del frumento, del riso, del vino, della
canapa. Altrettanta è la fecondità delle Marche, ma i possessori
meno ricchi s’accontentano delle produzioni meno costose, quali il
vino e la seta: il colono è a mezzerìa, non affittajuolo. Lo Stato
guadagna assai dalle saline di Cervia e di Comacchio.
L’inameno Appennino verso settentrione vestesi di foreste; ma di
sotto di Roma restò ignudo, dacchè Sisto V le fece distruggere per
togliere il nido ai masnadieri: da quelle che sopravanzano verso il
lago di Bolsena e le fonti del Tevere si taglia eccellente legname
anche da navi. Le valli interposte si lavorano a piccola coltura, e
bellissime quelle della Nera e del Velino: la scabra dell’Anio è atta
appena all’ulivo: verso il Napoletano si allargano i piani di Sacco. Le
rive del Tevere mostrano la piccola coltivazione fino al monte
Soratte, ove comincia l’Agro romano, vastità di ducencinquantamila
ettari ubertosissimi, ma che accumulati in possessioni non minori di
trecento ettari, e fino di cinquecentomila, spesso con una sola casa
rustica, la più parte rimane soda, o soltanto lavorata a lunghissimi
intervalli.
Nel medioevo le famiglie romane viveano alla campagna e de’
prodotti di questa, e se le guerre private vi recavano guasti,
adoperavasi però ogni cura a farle fruttare come unica ricchezza.
Quando i papi cominciarono a impinguare i nipoti, questi comprarono
i beni de’ piccoli proprietarj, che volentieri li cambiavano contro
luoghi di monte, oggi diremo azioni di banca, molto fruttuosi. Nel
1470 Sisto IV permise a qualunque avventiccio di seminare per
proprio conto un terzo del terreno che fosse rimasto sodo: tale idea
avevasi allora della proprietà! Sisto V nel 1585 con un milione di
scudi stabilì una cassa di credito agricola a favore de’ proprietarj
dell’Agro romano; ma ben poco vantaggiò. Intanto i Borghesi vi
comprarono da ottantamila terre, e Paolo V le decretava immuni da
confisca: i Barberini altrettanto, impiegandovi, si disse, cento milioni
di scudi. Così sparve la proprietà suddivisa, e molte famiglie di
Parma, Firenze, Urbino lasciavano le proprie terre per venire a
Roma a goder le rendite dei Monti; ma non tardarono ad accorgersi
d’aver ceduto il certo per l’incerto. Alessandro VII cominciò le
riduzioni d’interessi: onde il credito ebbe una scossa tanto maggiore
perchè la cosa era inusata, i capitali si ascosero o sparvero, e così la
terra appartenne a proprietarj cui mancavano i capitali da utilizzarla.
Scemata la produzione, si dovette assicurare il vivere alle
popolazioni col proibire l’asportazione; laonde l’agricoltura si
restrinse a produrre soltanto quant’era necessario per l’interno.
Oggimai quell’ampiezza era posseduta da centredici famiglie e
sessantaquattro congregazioni: i Borghesi davano a fitto
ventiduemila ettare, i Chigi cinquemila seicento, i Cesarini Sforza
undicimila, e così via, cavandone da otto a diciotto franchi l’ettare: e i
grandi fittajuoli sopperivano alle spese cui non basterebbero i
proprietarj. Nella stagione che l’aria è men micidiale, si fa ressa ad
ottenere le ricchezze del suolo; centinaja d’aratri, a quattro, a sei, a
otto paja di bufali di fronte lo solcano; quella che credevi una
sodaglia incolta, in pochi giorni trovasi arata e sementata; poi si
dimentica fino all’ora della messe, quando un nugolo di montanari
scende alla mietitura; e dove parea un mare di biade ondeggianti, in
pochi giorni non rimane spiga in piede, e sottentra aspetto di
deserto. La gente degli Abruzzi, compiuta l’opera, riporta a’ suoi
monti pochi denari e le febbri. Il resto si abbandona alla pastorizia
che frutta senza spese nè pericolo, ed offre un cibo sano e nutritivo
alla città: ma neppur le mandre si pensa a moltiplicare, o introdurvi
migliori specie di montoni e di cavalli, in modo da farne lontane
asportazioni. Un pastore sceso dalla montagna, a cavallo addirizza i
numerosissimi armenti, trafiggendo con un lancione il puledro o la
bufala che scompigli il branco; e pochi bastano a migliaja d’animali.
Di cui in tutto lo Stato contansi oggi quattro milioni ducentomila capi,
dove seicentosessantatremila sono bovini, quindicimila muli ed asini,
due milioni e mezzo di pecore, trecentoventimila capre,
settecentomila majali. Ecco perchè delle 4,166,297 ettare dello Stato
Pontifizio, 1,046,861 tengonsi a prati.
Le alture d’Albano che fanno cornice all’Agro romano, nutrono una
popolazione robusta, e d’uva e frutti provvedono la capitale: ma
neppur qui abbastanza si cerca migliorare le produzioni, e il vino e
l’olio.
Di là da Velletri cominciano le paludi Pontine su quarantadue
chilometri di lunghezza per diciotto di larghezza. Pio VI vi sanò
ottomila ettare, che furono distribuite in enfiteusi coll’obbligo di
coltivarle e mantenere i canali secondarj, ma non che adoprarvi tutta
la cura, è assai se s’adempiono i contratti. Principali concessionarj
sono le famiglie Massimo, Fiano, Gaetani, e la fabbrica di San
Pietro, alla quale appartiene il Campo Morto di ottomila cinquecento
ettare, dove, fra gli altri allettativi per attirar gente, i malfattori sono
tenuti immuni dalla giustizia purchè subiscano la disciplina
prescrittavi. Quel podere alla semenza di mille ettolitri di frumento e
quattrocentoventi d’altre granaglie risponde l’annuo ricolto di
quindicimila trecento ettolitri; quattrocento giornalieri lavorando alla

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Textbook Nanocatalysts in Environmental Applications 1St Edition Samira Bagheri Ebook All Chapter PDF

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Nanocatalysts in Environmental

Applications 1st Edition Samira Bagheri

Data Mining and Learning Analytics Applications in

Fundamentals of MALDI ToF MS Analysis Applications in

Medical Futility A Cross National Study 1st Edition

Nanomaterials in energy and environmental applications

Metalloenzymes in Denitrification Applications and

Studies on Time Series Applications in Environmental

Microbial Metabolomics Applications in Clinical

Environmental problems in marine biology methodological

ISSN 1865-3529 ISSN 1865-3537 (electronic)

© Springer International Publishing AG, part of Springer Nature 2018

Printed on acid-free paper

Kuala Lumpur, Malaysia Samira Bagheri

1 Enhanced Photocatalytic Activity by Using Modiﬁcation

2.2 Alteration on Structured of Photocatalysis System . . . . . . . . . . . . 26

4.4.3 Operation Parameters: Light Intensity . . . . . . . . . . . . . . . . 57

6.6 Real Implementations of Mixed Phase Titania in Mitigation

Samira Bagheri and Nurhidayatullaili Muhd Julkapli

1.1 Introduction: Basic Principles of Heterogeneous

S. Bagheri (B) · N. Muhd Julkapli

© Springer International Publishing AG, part of Springer Nature 2018 1

1.2 Activated Carbon

1.2.1 Characterization of Carbon Nanomaterials

Lately, carbon nanomaterials technology has made unexpected development due to

1.2.2 Transformation of Biomass to Carbon

Biomass conversion to carbon materials through catalytic approach normally begins

1.2.3 Catalytic Transformation of Biomass to Carbon

1.2.3.1 Homogeneous Catalyst

1.2.3.2 Heterogeneous Catalyst

The utilization of heterogeneous catalysis along with an immense range of designs

Solid Acid Catalyst

alkylation, acylation, esterification, dehydration, and isomerization of the ethanol

120), niobic acid, mixed oxides (silica–zirconia and silica–alumina), silica–niobia,

Crystalline microporous solids are an important part of zeolites because of its

Metal Ion Catalyst

Metal Oxide Catalyst

1.3 Photocatalytic Systems with Activated Carbon

The activated carbon is a carbonaceous material, which structured on plant-based

1.3.1 Effect of Surface Properties

adsorption photocatalysis substrate hybrid system was used in comparison with a

1.3.2 Activated Carbon/Transition Metal Oxide

1.3.2.1 Activated Carbon/Titania Photocatalysis System

Titania Photocatalysis System

The most promising semiconductor for photocatalytic destruction organic pollutants

powders contributed to some drawbacks in separating phase in photocatalysis, with

Titania/Activated Carbon Photocatalysis System

As a model of titania: activated carbon photocatalytic process can be more of a com-

1.3.2.2 Activated Carbon/ZnO Photocatalysis System

1.4 Activated Carbon Photocatalytic Systems: Future

1.4.1 Granular and Spherical Activated Carbon

Granule activated carbon supports titania powdered by adding more pollutants

1.4.2 ACF Photocatalysis System

1.4.3 Graphene/Titania Photocatalysis System

1.4.4 Titania/CNT Photocatalysis System

1.4.5 Titania: Activated Carbon Semiconductor Doped

1.4.6 Titania: Activated Carbon Nonmetal Doped

Doping of nonmetal, such as N, P, B, C, S, F, chlorine, and bromine, has been

Nei Liberali questo momentaneo agitarsi sotto le bajonette de’

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