bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxide Solid Solutions
Authors: Cimino Alessandro , Stone Frank S.
Published: March 2008

The sections in this article are

Introduction

Principles, Preparation, and Characterization

Principles

Preparation

Characterization

Bulk Composition and Structure

Surface Composition

Catalysis in the Context of Activity

N2ODecomposition,COOxidation andH2D2Equilibration

Combustion of Hydrocarbons

Perovskite Catalysts

Hexa‐Aluminate Catalysts

Ceria‐Containing Catalysts

Catalysis in the Context of Selectivity

Selective Oxidation

Reactions Involving Dehydrogenation, Hydrogenation, and Reforming

Catalysis in the Context of Surface Acidity and Basicity

Dehydration of Alcohols on Ionic Solid Solutions

Acid Catalysis by Aluminophosphates

Conclusions
Principles of Chemisorption
Authors: Freund Hans‐Joachim
Published: March 2008

The sections in this article are

Introduction

Thermodynamics and Energetics

Sticking

Surface Diffusion

Structure Sensitivity
Rates of Catalytic Reactions
Authors: Dumesic James A. , Huber George W. , Boudart Michel
Published: March 2008

The sections in this article are

Introduction

Turnover Rate/Turnover Frequency: Generalities

Comparison of Rate Data

Collection of Reaction Kinetics Data

Catalytic Cycles

Building Kinetic Models

Thermodynamic Consistency

Transition State Theory and Entropies of Surface Species

Formulation of Kinetic Models in Terms of Transition States

Degree of Rate Control/Rate‐Determining Step

Conditions for Catalyst Optimality
Dynamics of Surface Reactions
Authors: Ertl Gerhard
Published: March 2008

The sections in this article are

Introduction

Energy Exchange between Adsorbate and Solid

Limitations of Transition State Theory

Sticking

Collision‐Induced Surface Reactions

L
angmuir–
H
inshelwood versus
E
ley–
R
ideal Mechanisms

“Hot” Adparticles

Particles Coming off the Surface

Electronic Excitations Caused by Surface Reactions

Surface Reactions Initiated by Electronic Excitations
Non‐Linear Dynamics: Oscillatory Kinetics and Spatio‐Temporal Pattern Formation
Authors: Ertl Gerhard
Published: March 2008

The sections in this article are

Introduction

From the Atomic to the Mesoscopic Scale: Spatio‐Temporal Self‐Organization in the Catalytic Oxidation of Hydrogen on aPt(111) Surface

Overview of the Theoretical Background

COOxidation onPt(110): A Case Study of a Uniform Isothermal System

Oxidation of Carbon Monoxide on Other Surfaces

Other Isothermal Systems with Oscillatory Kinetics

Thermokinetics

Composite Surfaces

Microscopic Scale Processes

Controlling the Kinetics
Substituent Effects
Authors: Kraus Milos , Knözinger Helmut
Published: March 2008

The sections in this article are

Substituent, Reaction Center, and Surface Reaction Complex

Mass and Specific Effects of Substituents

Mass Effect

Electronic Effects

Steric Effects

Quantitative Treatment of Substituent Effects

Empirical Correlations

Linear Free‐Energy Relationships

Reliability of Linear Correlations

Catalyst Characterization by the Slopes of
LFER

Substituent Effects as a Tool for Elucidation of Mechanisms

Cracking of Alkylbenzenes

Hydrogenation of Alkenes on Metals

Dehydration of Alcohols on Oxides

Hydrotreating Reactions

Prospects
Promoters and Poisons
Authors: Koel Bruce E. , Kim Johoo
Published: March 2008

The sections in this article are

Introduction

Modifiers in Catalysis

Structural Modifiers

Bonding Modifiers

Promoters and Poisons for Some Important Catalytic Reactions

Steam Reforming

A
Reactive Sites on
Ni
Catalysts

B
Alkali and Alkaline Earth Promoters for
Ni
Catalysts

C
Sulfur Poisoning of
Ni
Catalysts

Water‐Gas Shift Reaction

A
Iron‐Based Catalysts: High‐Temperature Shift Catalysts

a 
Structural Modifiers in Iron‐Based Catalysts

b 
Metal and Metal Oxides as Promoters for Catalytic Activity

B
Copper‐Based Catalysts: Low‐Temperature Shift Catalysts

a 
Structural Modifiers

b 
Cesium Modifiers

c 
Sulfur Poisoning

Methanation

A
Active Phase and Structural Modifiers

B
Electropositive Modifiers

C
Electronegative Modifiers

F
ischer–
T
ropsch Synthesis

A
Fe
‐Based Catalysts

a 
Active Phase and Structural Modifiers

b 
Metal Modifiers

c 
Sulfur Modification

B
Co‐Based Catalysts

a 
Electropositive Modifiers

b 
Electronegative Modifiers

Ammonia Synthesis

A
Summary of Iron Ammonia Synthesis Catalysts

B
Ruthenium Catalysts for Ammonia Synthesis

a 
Active Phase and Structural Modifiers

b 
Metal Modifiers

c 
Poisoning Modifiers

Case Studies of the Fundamental Basis of Modifier Action in Catalysis

Ca promotion in
Pd
/
Si
O
2
Catalysts for Methanol Synthesis

Direct Formation of Hydrogen Peroxide

A
Pd
Catalysts for Direct
H
2
O
2
Synthesis

B
Promotion Effects of Halide Anions

Methane Reforming on
Au

Ni
Catalysts

A
Recent Studies on
Ni
Catalysts for Methane Reforming

B
Methane Reforming on
Au
‐Modified
Ni
Catalysts

Oxidative Dehydrogenation of Alkanes

A
Effects of Supports, Loading, and Preparation

B
Effect of Alkali Metal Additives on Vanadia Catalysts
Computer Simulations of Shape Selectivity Effects
Authors: Smit Berend , Maesen Theo M.
Published: March 2008

The sections in this article are

Introduction

Conventional Hydroconversion Mechanisms

Basic Mechanism

Shape Selectivity: General Principles

ATransition‐State Shape Selectivity

BReactant Shape Selectivity

CProduct Shape Selectivity

DExterior Surface Shape Selectivity

EOther Forms of Shape Selectivity

Molecular Simulations

Simulation Techniques

AMolecular Dynamics of Adsorbed Molecules

BMonteCarlo Simulation of Adsorbed Molecules

CConfigurational‐BiasMonteCarlo Technique

DRare Event Simulations

Intermolecular Potentials

AZeolite–Zeolite Interactions

BAdsorbate–Adsorbate Interactions

CZeolite–Adsorbate Interactions

Free Energy Model

Introduction

Conventional Shape Selectivity

Transition‐State and Reaction‐Intermediate Shape Selectivity

Reactant Shape Selectivity

Product Shape Selectivity

Concluding Remarks

Acknowledgments
Rate Procurement and Kinetic Modelling1A list of symbols used in the text is provided at the end of the chapter.
Authors: Kapteijn Freek , Berger Rob J. , Moulijn Jacob A.
Published: March 2008

The sections in this article are

Introduction

Rate Procurement—Types of Laboratory Reactors

Kinetic Modeling

Rate Expression

Derivation of the Rate Expression

Characteristics of the
LHHW
Rate Expression

Adaptation of
LHHW
Models and Other Models

Deactivation Kinetics

Parameter Estimation—Model Discrimination

Data Regression

Maximum Likelihood and Variance Models

Linear Regression

Nonlinear Regression

Kinetic Data Handling

Model Testing

Statistical Testing—Model Adequacy

Statistical Testing—Parameter Significance

Statistical Testing—Residual Distribution

Physicochemical Testing—Kinetic Parameters

Physicochemical Testing—Site Density

Discrimination Between Rival Models

Model Discrimination—Initial Rate Expressions

Model Discrimination—Diagnostic Parameters

Model Discrimination—
B
artlett's Chi‐Squared Test

Sequential Experimental Design

Discrimination Between Rival Models—Design Criterion

Parameter Improvement

Parameter Improvement—

D

Optimality (Minimum Volume Design)

Parameter Improvement—

E

Optimality (Shape Design)

Improved Parameter Estimation—

A

Optimality

Improved Parameter Estimation—Other Criteria

Flowsheet for Sequential Experimental Design

Multi‐response Models

Computer Codes and Software Packages

Conclusion

List of Symbols
11C,13Nand15OPositron (β+) Emitters in Catalysis Research
Authors: Hensen Emiel J. M. , Jonkers Gert , van Santen Rutger A.
Published: March 2008

The sections in this article are

Introduction

Characteristics of β‐Emitters

Production of Labeled Material

11CO,11CO2,11CH3C5H11

13NO,13NH3

15OO,N215O

Detection of β‐ and Annihilation Radiation

Applications in Heterogeneous Catalysis

Tracer Exchange Positron Emission Profiling (TEX‐PEP)

Ammonia Oxidation onPt

Conclusions
Computational Fluid Dynamics Simulation of Catalytic Reactors
Authors: Deutschmann Olaf
Published: March 2008

The sections in this article are

Introduction

Modeling of Reactive Flows

Governing Equations of Multicomponent Flows

Turbulent Flows

Homogeneous Chemical Reactions in the Gas Phase

Modeling Surface Reaction Rates

Coupling with the Flow Field

Modeling the Surface Reaction Rate

Mean Field Approximation and Reaction Kinetics

Development of Multi‐Step Surface Reaction Mechanisms

Limitation of the Models and Alternative Approaches

Model Evaluation

Transport and Reactions in Porous Media

Momentum and Energy Equations for Porous Media

Reaction–Diffusion Equation

Dusty Gas Model

Numerical Methods and Computational Tools

Numerical Methods for the Solution of the Governing Equations

CFDSoftware

Solvers for StiffODEandDAESystems

Reactor Simulations

Flow Through Channels

Monolithic Reactors

Fixed‐Bed Reactors

Wire Gauzes

Catalytic Reactors with Multi‐Phase Fluids

Summary and Outlook

Acknowledgments
Electrochemical Modification of Catalytic Activity
Authors: Vayenas Constantinos G. , Katsaounis Alexandros , Brosda Susanne , Hammad Ahmad
Published: March 2008

The sections in this article are

Introduction

Catalytic and Electrocatalytic Kinetics

Solid Electrolytes

Solid Electrolyte Potentiometry (SEP)

Electrocatalytic Operation of Solid Electrolyte Cells

Electrochemical Promotion of Catalysis

Selectivity Modification and Promotional Effects on Chemisorption

Selectivity Modification

Promotional Effects on Chemisorption

Basic Questions

Origin of Electrochemical Promotion

Magnitude of Electrochemical Promotion and the Sacrificial Promoter Mechanism

Mechanism of Metal–Support Interactions

Interrelation of Promotion, Electrochemical Promotion and Metal–Support Interactions: the Double‐Layer Model of Catalysis

Why the “New” Supports?

Double‐Layer Approach to Catalysis

Why Double Layer? Rationalization and Prediction of Desired Types of Promoters and Supports

The Four Types of Rate–Work Function Dependence and the Promotional Rules

Double‐Layer Isotherms and Kinetics

Electropromotion of Thin Films and Electropromoted Monolithic Reactors

Summary and Perspectives

Outlook
Photocatalysis: Development of Highly Functional Titanium Oxide Photocatalysts
Authors: Takeuchi Masato , Kitano Masaaki , Matsuoka Masaya , Anpo Masakazu
Published: March 2008

The sections in this article are

Introduction

Ion Engineering Techniques for the Preparation of Well‐Defined TiO2Photocatalysts

Visible Light‐Responsive TiO2Photocatalysts

Modification of the Electronic Properties of TiO2Semiconducting Fine Powder Photocatalysts by an Advanced Metal Ion Implantation Method

Preparation of Highly Transparent TiO2Thin‐Film Photocatalysts

Preparation of Visible Light‐Responsive TiO2Thin‐Film Photocatalysts byRF‐Magnetron Sputtering (RF‐MS) Deposition in a Single Process

Photo‐induced Superhydrophilic Properties on the Surface of the TiO2Thin‐Film Photocatalysts

Conclusions
Laboratory Catalytic Reactors: Aspects of Catalyst Testing1A list of symbols used in the text is provided at the end of the chapter.
Authors: Kapteijn Freek , Moulijn Jacob A.
Published: March 2008

The sections in this article are

Introduction

Reactor Systems

Classification

Types of Laboratory Reactors

Gas–Solid and liquid–Solid Reactions

Gas–Liquid–Solid Reactions

Design Equations

CSTR

PFR

Summary of Laboratory Systems

Mass and Heat Transfer

Extraparticle Gradients

Intraparticle Gradients

Catalyst Bed Gradients

Gas–Liquid Mass Transfer

Comparison of Criteria

Mass Transport

Heat Transport

Effect of Transport Limitations on Observed Behavior

Diagnostic Experimental Tests

Extraparticle Concentration Gradients

Intraparticle Concentration Gradients

Temperature Gradients

Proper Catalyst Testing and Kinetic Studies

Current Trends in Catalyst Testing

Parallelization/High‐Throughput Experimentation

Miniaturization
Catalytic Fixed‐Bed Reactors
Authors: Eigenberger Gerhart
Published: March 2008

The sections in this article are

Introduction

Catalyst Shapes for Fixed‐Bed Reactors

Random Packings

Monoliths

Gas Flow and Pressure Drop in Fixed Beds

Heat Transfer in Catalyst‐Filled Tubes

Comparison of Different Catalyst Shapes

Types of Fixed‐Bed Reactor

Adiabatic Reactors

Multi‐Stage Reactors

Cooled or Heated Multitubular Fixed‐Bed Reactors

Heat‐Transfer Media

Design Concepts for Exothermic Reactions

Design Concepts for Endothermic Reactions

Reaction Control by Controlling the Heat‐Transfer Medium Temperature

Reaction Control through Catalyst Activity Profile

Multifunctional Fixed‐Bed Reactors

Heat‐Integrated Reactors

Heat‐Integrated Reactors for Exothermic Reactions

Heat‐Integrated Reactors for Endothermic Reactions

Sorptive and Membrane Reactor Concepts

Safety Issues of Fixed‐Bed Reactors

Parametric Sensitivity and Run‐Away

Wrong‐Way Behavior and Transient Run‐Away

Decoking of Fixed‐Bed Reactors

Other Safety Aspects

Conclusions
Fluidized‐Bed Reactors1A list of abbreviations/acronyms used in the text is provided at the end of the chapter.
Authors: Werther Joachim
Published: March 2008

The sections in this article are

Introduction

The Fluidization Principle

Forms of Fluidized Beds

Advantages and Disadvantages of the Fluidized‐Bed Reactor

Fluid‐Mechanical Principles

Minimum Fluidization Velocity

Fluidization Properties of Typical Bed Solids

Gas Distribution

Gas Jets in Fluidized Beds

Bubble Development

Elutriation

Circulating Fluidized Beds

Catalyst Attrition

Gas Mixing in Fluidized‐Bed Reactors

Gas Mixing in Bubbling Fluidized Beds

Gas Mixing in Circulating Fluidized Beds

Gas–Solid Separation

Injection of Liquid Reactants into Fluidized Beds

Industrial Applications

Heterogeneous Catalytic Gas‐Phase Reactions

Polymerization of Alkenes

Modeling of Fluidized‐Bed Reactors

Bubbling Fluidized‐Bed Reactors

Circulating Fluidized‐Bed Reactors

New Developments in Fluidized‐Bed Reactor Modeling

Scale‐Up

Bed Diameter

Grid Design

Internals

Catalyst Particle‐Size Distribution

Secondary Reactions in the Freeboard

Catalyst Attrition

Other Factors

Conclusions

List of Symbols
Slurry Reactors1A list of symbols used in the text is provided at the end of the chapter.
Authors: Nedeltchev Stoyan , Schumpe Adrian
Published: March 2008

The sections in this article are

Introduction

Types of Slurry Reactor

Slurry Bubble Column Reactor

Other Reactor Types

Hydrodynamics of Slurry Reactors

Flow Regimes

Minimum Suspension Conditions

Average Bubble Diameter

Backmixing

Gas Holdup

Bubble Rise Velocity

Mass Transfer in Slurry Reactors

Volumetric Liquid‐Side Mass‐Transfer Coefficient (
k
L
a
)

k
L
a
in the Slurry Bubble Column

k
L
a
in the Stirred Tank

Gas–Liquid Specific Interfacial Area (
a
)

Liquid‐Side Mass‐Transfer Coefficient at the Gas–Liquid Interface (
k
L
)

Gas‐Side Mass‐Transfer Coefficient (
k
G
)

Liquid‐Solid Mass‐Transfer Coefficient (
k
S
)

Enhancement of Gas–Liquid Mass Transfer

Adsorptive Transport (“Shuttle Mechanism”)

Absorption with Heterogeneous Catalytic Reaction

Reactive Particles

Optimum Catalyst Size

Heat Transfer in Slurry Reactors

Concluding Remarks

Acknowledgments
Catalytic Distillation
Authors: Miracca Ivano , Judzis Arvids , Sahay Nishit , Sanfilippo Domenico
Published: March 2008

The sections in this article are

Introduction

Potential versus Constraints

Practical Realization of Catalytic Distillation

Tray Towers

Packed Towers

Modeling Catalytic Distillation

Equilibrium‐Stage Models

Rate‐Based Models

Selected Processes

Future Perspectives
Automotive Exhaust Treatment1A list of abbreviations/acronyms used in the text is provided at the end of the chapter.
Authors: Lox Egbert S. J.
Published: March 2008

The sections in this article are

Introduction

Origin of Emissions

Importance of Road Transport

Legislation

History

Present and Future

Measurement of Emissions

Passenger Cars and Light Duty Vehicles

Heavy Duty Trucks and Buses

Technology to Meet Legislation

Spark‐Ignition Engines

Compression‐Ignition Engines

Catalytic Systems for Gasoline‐Fueled, Indirect Injection Spark‐Ignition Engines

Introduction

Engine‐Out Emissions

Reactions

Emission Control Concepts

Aspects of Three‐Way Catalyst Design

General Aspects

Bead Catalysts

Ceramic Monolithic Substrates

Metallic Monolithic Substrates

Washcoat

Precious Metals

Aspects of Three‐Way Catalyst Performance

Introduction

Measurement of Catalyst Performance

Influence of Catalyst Operating Conditions

Influence of Substrate and Converter Design

Influence of Catalyst Formulation

Deactivation of Three‐Way Catalysts

Introduction

Assessment of Durability

Selected Deactivation Phenomena

Future Developments and Concepts

Catalytic Systems for Gasoline‐Fueled Direct Injection Spark‐Ignition Engines

Introduction

Aspects of Operation ofNOx‐Adsorber Systems

Aspects of Deactivation ofNOx‐Adsorber Systems

Catalytic Systems for Diesel‐Fueled Compression‐Ignition Engines

Introduction

Diesel Oxidation Catalysts

Aspects of Diesel Oxidation Catalyst Design

Aspects of Deactivation

Future Developments and Concepts

Catalytic Diesel Particulate Filter Systems

Aspects of Diesel Filter System Design

Aspects of Filter System Operation

DieselNOx‐Reduction Systems

Introduction

HC‐DeNOx‐Systems

DieselNOx‐adsorber systems

SCRSystems

Future Developments and Concepts

Conclusions and Outlook

Acknowledgments

List of Abbreviations and Symbols
Catalytic Dehalogenation
Authors: Howe Russell Francis
Published: March 2008

The sections in this article are

Introduction

Organohalogen Compounds

Reaction Types

Decomposition

Hydrodehalogenation

Oxidation

Hydrolysis

Supported Metal Catalysts

Zeolite Catalysts
Catalytic Routes to Hydro(chloro)fluorocarbons
Authors: Ainbinder Zarah , Manzer Leo E. , Nappa Mario J.
Published: March 2008

The sections in this article are

Background

Catalytic Transformations

Addition ofHF

Halogen Exchange

Isomerizations

Disproportionations/Conproportionations

HXElimination Reactions

Hydrodehalogenations/Dehydrohalogenations

Oxygenates as Reactive Intermediates

Coupling

Chlorinations/Chlorofluorinations

CFCDestruction

Purification Techniques

Opportunities for the Future

Conclusions
Catalysis in Water Remediation
Authors: Prüße Ulf , Thielecke Nadine , Vorlop Klaus‐Dieter
Published: March 2008

The sections in this article are

Introduction

Oxidation Processes

Wet Air Oxidation (WAO)

Conventional Wet Air Oxidation

Supercritical Water Oxidation

Catalytic Wet Air Oxidation (CWAO)

Fenton Processes

Conventional Fenton Processes

Photo‐Assisted Fenton Processes

Applications of Fenton Processes

Photocatalysis

Other Oxidation Processes

Reduction Processes

Hydrodechlorination/Hydrodehalogenation

Hydrodechlorination by Zero‐Valent Metals

Hydrodechlorination with Supported Metal Catalysts

Hydrodenitration

Conclusions
Ammonia Synthesis
Authors: Schlögl Robert
Published: March 2008

The sections in this article are

Introduction

Some Basic Considerations

Catalyst Materials: Iron and Ruthenium

Ammonia Synthesis as the Reference Reaction

Choice of Catalyst: Historic Development

Choice of Catalyst: Theory‐Based Approach

Reaction Efficiency and Research Needs

Thermodynamic Aspects

Di‐Nitrogen

Nitrides

Hydrogen

The Reaction

Phase Diagrams

Ruthenium Substrates

Generation and Structure of “Ammonia Iron”

Reference Experiments

Structure of the Oxide Precursor

Activation Process

Activated Catalyst: Microtexture

Activated Catalyst: Microstructure

Nature of the Iron Catalyst

Abundance of Active Sites

Single Crystal Approach in the Iron System

Single‐Crystal Structures

Energetics of Hydrogen and Nitrogen Chemisorption

Structure and Energetics of Chemisorbed Ammonia

Kinetics of Nitrogen Chemisorption

Potassium Promoter Effect

Polycrystalline Substrates

The Material Gap: Alumina as Promoter

Nitrogen Chemisorption on Model Systems

Nitrogen Chemisorption on Polycrystalline Substrates

Non‐Fe Systems:RuCatalysts

NanostructuredRu

Surface‐Science Studies of theRuSystem

Mechanism of Ammonia Synthesis

Basic Kinetic Information

Analytical Rate Expressions

Microkinetic Models

Conclusions
Hydrocyanic Acid (HCN) Production
Authors: Sauer Jörg , Bewersdorf Martin , Köstner Martin , Rinner Michael , Wolf Dorit
Published: March 2008

The sections in this article are

Introduction

TheAndrussow Process

History

Fundamentals

Production of Liquid Hydrocyanic Acid

Pressure Variant

Oxygen Variant

Ammonia Recycling

Reactor and Catalyst

TheBMAProcess

Overview

Development of the Catalyst

Development of theBMATubes

Reactor Design

Mechanism and Kinetics ofHCNformation in theBMAandAndrussow Processes

Kinetics and Mechanism of theBMAProcess

Thermodynamic Context

HCNandN2Formation

Coke Formation

On the Role of Gas‐Phase Reactions

Catalytically Active Centers

Kinetics and Mechanism of theAndrussow Process

Thermodynamic Relationships

HCNFormation

HCNHydrolysis

Catalytically Active Centers

Final Remarks
Oxidation of Sulfur Dioxide
Authors: Näumann Fritz , Schulz Matthias
Published: March 2008

The sections in this article are

Introduction

The Contact Process

Thermodynamic Considerations

Reaction Mechanisms and Kinetics

Sulfur Dioxide as the Basis of Sulfuric Acid Production

Classical Sulfuric Acid Production

Sulfur Dioxide from Combustion of Elemental Sulfur

Sulfur Dioxide from Roasting of Pyrite

Sulfur Dioxide from Metallurgical Plants

Copper Smelting

Zinc Blende Roasting

Nickel Sulfide and Lead Sulfide

Sulfur Dioxide from Decomposition of Acid

Sulfur Dioxide from Combustion of H
2
S

Sulfur Dioxide from Sulfates

Decomposition of Gypsum (
M
üller–
K
ühne Process)

Decomposition of Iron Sulfate

Sulfuric Acid from Sulfur Dioxide in Tail Gases from Power Stations

The Contact Process: Practical Application

Fundamentals

Single Absorption Catalysis

Double Absorption Catalysis

Pressure Catalysis

Fluidized‐Bed Technology

The Catalyst

Catalyst Production

Catalyst Requirements

Disposal of Spent Catalyst
Hydrotreating
Authors: Prins Roel
Published: March 2008

The sections in this article are

Introduction

Reaction Mechanisms

Hydrodesulfurization

Hydrodenitrogenation

Hydrodeoxygenation

Hydrodechlorination

Hydrotreating of Mixtures

The
C

X
Bond Breaking Mechanism

Catalyst Structure

Structure of the Oxidic Catalyst Precursor

Structure of the Sulfidic Catalyst

Structure of
Mo

Structure of the Promoter

Surface Sites

Modifiers

Structure–Reactivity Relations

Hydrotreating Technology

Catalysts

Reactor Systems

FCC
Naphtha Hydrotreating

Direct Hydrotreating

Pre‐ or Post‐octane Upgrading

Diesel Hydrotreating

Other Desulfurization Technologies

The Future of Hydrotreating
Hydrodemetalation
Authors: Wei James
Published: March 2008

The sections in this article are

Introduction

Metal Compounds in Petroleum

Residue Hydrotreating Technology

Reaction Kinetics and Diffusion in Catalytic Hydrodemetalation

Model Compound Kinetic Studies

Model Compound Diffusion

Intraparticle Metal Deposition Profiles

Hydrodemetalation of Petroleum Oils and Residua

Catalyst Deactivation

Conclusions
Catalytic Reforming
Authors: Moser Mark D. , Bogdan Paula L.
Published: March 2008

The sections in this article are

Introduction

The Chemistry of Reforming

Feed Composition and Characteristics

Reforming Products

Reforming Reactions

Reforming Catalysts

General Aspects

Catalyst Regeneration

Reforming Processes

Process Variables

Commercial Catalysts

Modeling/Optimization of Commercial Reforming Units

Process Flow Schemes

Future Developments
Fluid Catalytic Cracking
Authors: Cheng Wu‐Cheng , Habib E. Thomas , Rajagopalan Kuppuswamy , Roberie Terry G. , Wormsbecher Richard F. , Ziebarth Michael S.
Published: March 2008

The sections in this article are

Introduction and Overview

History

FCCToday

Position in a Modern Petroleum Refinery

Environmental Issues

FCCUnit Hardware and Operations

Unit Types

Heat Balance

Modes of Operation

Regeneration Mode—Partial Burn vs. Full Burn

Resid Processing

Petrochemical Mode (Light Olefins)

FCCFeeds

Sources and Trends

Molecular Types

Characterization

Effects onFCCUnit Operation

Conradson Carbon and Feed Heaviness

Feedstock Composition

Metals:Ni,V,NaandFe

Sulfur

Nitrogen

The Chemistry of Catalytic Cracking

Carbocations

Formation of Carbocations

Isomerization Reactions

CarbonCarbon Bond Breaking by Beta‐Scission

Hydride Transfer (also Referred to as Hydrogen Transfer)

Heteroatom Chemistry: Sulfur

FCCCatalysts

Description and Formulation

Zeolite Component

Zeolite Modifications

Zeolite Activity and Selectivity Effects

Matrix

Commercial Matrices

Effect of Matrix on Selectivity

Characterization

ZSM‐5 Additives

FCCUEnvironmental Emissions Controls

Overview—Catalyst Versus Hardware

Particulates

Carbon Monoxide (CO)

Sulfur Oxides (SOx)

Nitrogen Oxides (NOx)

Laboratory Evaluations and Pilot Plant Testing

Accelerated Aging of Catalysts

Simulation of Metals Poisoning

Reactor Types—Fixed Bed vs. Fluid Bed vs. Transport Phase

Temperature Profile and Isothermal vs. Adiabatic Testing

Summary and Future Trends in Catalytic Cracking
Hydrocracking and Catalytic Dewaxing
Authors: van Veen J. A. Rob , Minderhoud Johannes K. , Huve Laurent G. , Stork Wim H. J.
Published: March 2008

The sections in this article are

Introduction

Hydrocracking

Processes and Process Configurations

Two‐Stage Hydrocracking

Single‐Stage Hydrocracking

Alternative Process Schemes

Mild Hydrocracking

Reactor Design Aspects

Feedstocks

Products

Catalyst Systems

HCCatalyst Design Rules

Coke Deactivation

Zeolite‐Based Catalysts

Effect of Recycle Operation

New Catalyst Developments

Ring Opening

Catalytic Dewaxing

Commercial Developments

Shape‐Selective Catalysis

Dewaxing Catalysts

Reaction Pathway

Process Line‐Ups

Cracking Dewaxing

Isomerization Dewaxing

Future Trends in Catalytic Dewaxing—the Gas to Liquid Route
Isomerization
Authors: Sie Swan Tiong
Published: March 2008

The sections in this article are

Introduction

Mechanism of Skeletal Isomerization ofC5+Alkanes with Acid Catalysts

Reaction Cycle in Isomerization of Alkanes

The Isomerization Reaction: Rearrangement of the Intermediate Carbenium Ion

Supporting Evidence for the Protonated Cyclopropane (PCP) Isomerization Mechanism

Reactions withn‐Butane

Effect of Chain Length on the Relative Rates of Isomerization ofn‐Alkanes

Location of Branching in Isomerized Alkanes

Chain Termination Reactions: Catalyst Deactivation

Acid‐catalyzed Cracking and Isomerization: Effect of Chain Length on Selectivity for Isomerization

Mechanism ofC4Alkane Isomerization

Isomerization Catalysts

Monofunctional Acidic Catalysts

Bifunctional Catalysts

Isomerization of Pentanes and Hexanes for Octane Enhancement

Octane Numbers and Thermodynamic Equilibrium Concentrations of Isomeric Pentanes and Hexanes

Processes for Isomerization of Pentanes and Hexanes

Processes Using Aluminum Chloride/Hydrochloric Acid as Monofunctional Catalyst

Processes Using Bifunctional Catalysts Consisting ofPtSupported on Chlorinated Alumina

Processes Using a Noble Metal on Amorphous Silica–Alumina as Bifunctional Catalyst

Processes Using a Noble Metal on Zeolite as Bifunctional Catalyst

CombiningC5andC6Alkane Isomerization with Physical Separations

Processes for Isomerization of Higher Alkanes

Processes for Conversion ofn‐Butane to Isobutane

Role of Alkane Isomerization in the Hydrocarbon Processing Industry
Oligomerization
Authors: O'Connor Cyril T.
Published: March 2008

The sections in this article are

Introduction

Background

Fundamentals

Mechanism of Alkene Oligomerization

Thermodynamics of Alkene Oligomerization

Kinetics of Alkene Oligomerization

Catalysts Used in Alkene Oligomerization

Zeolites

Mesoporous Catalysts

Other Acid Catalysts

Catalysts Incorporating Metals

Industrial Applications of Alkene Oligomerization

Zeolite‐Based Processes

Catpoly Process

Dimerization Processes

Conclusions
Etherification
Authors: Krause A. Outi I. , Keskinen Kari I.
Published: March 2008

The sections in this article are

Scope

Introduction and History of Tertiary Ethers

Chemistry

Main Etherification Reactions

Most Important Side Reactions

Thermodynamics of Ether Reactions

Kinetic Models

Other Ethers

Heavier Ethers

C
8
Alkenes

Higher Alcohols

Polyfunctional Ethers

Catalysts

Acidic Ion‐Exchange Resins

Zeolites and Modified Zeolites

Other Acidic Catalysts

Catalyst Deactivation

Raw Materials and Products

Typical Raw Materials

Feed Stream Treatment

Ether Products

Hydrocarbon Products

Processes

Operating Conditions

Processes for
MTBE
Production

Conventional
MTBE
Units

Reactive Distillation in
MTBE
Production

Processes for
ETBE
Production

Conversion of
MTBE
Plants for
ETBE
Production

Processes for
TAME
Production

Multipurpose Processes for Production of Ethers

Diesel Ethers

Dimethyl Ether

Properties of Dimethyl Ether

Processes for Dimethyl Ether Production

Di‐
n
‐Pentyl Ether

The Future
Methanol Synthesis
Authors: Hansen John Bøgdil , Højlund Nielsen Poul Erik
Published: March 2008

The sections in this article are

Introduction

Thermodynamics

Methanol Synthesis Catalysts

Introduction

Zn
O
/
Cr
2
O
3
Catalyst

Copper‐Based Catalysts

Cu
/
Zn
O
+ Element (
Al
,
Cr
, … )

Promotion of
Cu
/
Zn
O
/
MOx
Catalysts

Cu
/
Zr
O
2

Other
Cu
,
Cu
/
Me
,
Cu
/
Me
Ox
Catalysts

Pd
‐Based Catalysts

Sulfide Catalysts

Other Catalysts

Activation of
Cu
/
Zn
Catalyst

Activity as a Function of the Nature of Copper‐Based Catalysts

Catalyst Deactivation

Sintering

Sulfur Poisoning

Other Poisons

By‐Product Formation

Reaction Mechanism(s) and Active Sites

Cu
+
in a
Zn
O
Matrix as the Active Center

The
S
chottky Junction Theory

Partly Oxidized Copper Independent of Support as Active Sites

Metallic Copper in Dynamic Interaction with the Support

Cu
–Zinc Surface Alloy Model

Water Gas Shift Reaction

Kinetics

Reaction Rate Equations

Diffusion Restrictions

Kinetics in Slurry Phase Methanol Synthesis

Methanol Synthesis Technology

Synthesis Gas Preparation

Natural Gas Reforming

Adiabatic Pre‐Reforming

Tubular, Fired Reforming

Autothermal Reforming and Oxygen‐Fired Secondary Reforming

Gasification of Heavy Oil, Coal or Biomass

Coproduction in Ammonia Plants and Use of Off‐gases

Economics of Synthesis Gas Preparation

Reactor Systems and Synthesis Loop Layout

Slurry Phase Reactor Types

Methanol Purification

Concepts Circumventing the Equilibrium Limitations

Other Methanol Synthesis Routes and Technologies

Methanol Synthesis by Methane Activation

Conclusion
Methanol‐to‐Hydrocarbons
Authors: Kvisle Steinar , Fuglerud Terje , Kolboe Stein , Olsbye Unni , Lillerud Karl Petter , Vora Bipin V.
Published: March 2008

The sections in this article are

Introduction

IndustrialMTHDrivers

Monetization of Remote Natural Gas

Light Olefins: Supply and Demand

Methanol Technology

MTHCatalysis

Catalyst Systems

Reactions and Products

Catalyst System Properties and Modifications

Reaction Mechanisms

CarbeneCarbenoid Mechanisms

Carbocationic Mechanisms

Trimethyloxonium Intermediacy

Radical Mechanisms

The Hydrocarbon Pool

Product Formation

Parallel Reactions

Coke Formation

Reaction Kinetics

Reactor Technology

Process Descriptions

UOP/HydroMTOProcess

Integration ofMTOwith Olefin Cracking

LurgiMTP®Process

ExxonMobilMTOTechnology

Development and Commercial Status of theMTHProcesses

MobilMTG

UOP/HydroMTOProcess

LurgiMTP®Process

ExxonMobil

GTOProject Scenarios

MTOandGTOEconomics

CO2Aspects

Conclusions
Catalysis in Coal and Carbon Gasification
Authors: Radovic Ljubisa R.
Published: March 2008

The sections in this article are

Introduction

Processes

Catalysts

Mechanisms

Conclusion
Fuel Cells
Authors: Gasteiger Hubert A. , Garche Jürgen
Published: March 2008

The sections in this article are

Introduction

Working Principles of Fuel Cells

Cell and Stack Construction

Alkaline Fuel Cells (AFCs)

Proton Exchange Membrane Fuel Cell (PEMFC)

AHydrogen Proton Exchange Membrane Fuel Cell

BDirect Methanol Fuel Cell (DMFC)

Phosphoric Acid Fuel Cell (PAFC)

Molten Carbonate Fuel Cell (MCFC)

Solid Oxide Fuel Cell (SOFC)

Fuels for Fuel Cells

Thermodynamics and Kinetics of Fuel Cells

Low‐Temperature Fuel Cells with Gaseous Reactants

Electro‐Oxidation of PureH2

AFundamentalH2Oxidation and Evolution Kinetics

BVoltage Losses Due toH2Oxidation Kinetics in Low‐Temperature Fuel Cells

AnodicH2Oxidation in the Presence ofCOContamination

APractical Aspects of Fuel Cell Operation withCO‐ContaminatedH2

BCOTolerance Mechanisms onPtAlloys

CNew Research Directions for ImprovedCO‐Tolerant Anode Catalysts

Oxygen Reduction Reaction

AOxygen Reduction Kinetics and Kinetic Losses inH2/Air Fuel Cells

BQuantification of a Catalyst'sORRActivity inPEMFCs

CORRActivity inPAFCsorH3PO4/PBI‐Based MembranesFCs

DORRActivity inPEMFCsCompared with DiluteHClO4

EPtParticle Size Effect on theORRActivity

FORRMechanism

GPtAlloys and OtherORRCatalysts

Catalyst and Catalyst‐Induced Degradation Mechanisms

ADissolution of Cathode Catalyst Constituents

BCarbon Support Corrosion

CImpact of Contaminants

DH2O2andOHRadical‐InducedPFSADegradation

Fuel Cells for Direct Oxidation of Liquid Fuels

Direct Methanol Fuel Cells

AState‐of‐the‐ArtDMFCPerformance Limitations

BAnode Catalyst Performance Limitations

CDMFCPerformance Limit with CurrentPtRuCatalysts

DMethanol Electro‐Oxidation Mechanism

EPtRuCatalyst Modifications and Alternative Catalysts

FMethanol‐Tolerant Cathodes

Direct Ethanol Fuel Cells

Direct Formic Acid Fuel Cells

Fuel Cell Applications

General

Transportation Applications

Stationary Application

Portable Applications

Final Comments

Acknowledgments
Non‐Oxidative Activation of Alkanes
Authors: Traa Yvonne
Published: March 2008

The sections in this article are

Introduction

Thermodynamic Aspects

Activation of Methane

Catalytic Decomposition of Methane to Hydrogen and Carbon

Conversion of Methane to Ethane and other Aliphatics

Aromatization of Methane

The Catalyst

The Carbonaceous Deposits and Mechanistic Considerations

Influence of Co‐Reactants

Co‐Conversion of Methane with Alkenes

Alkylation of Aromatics with Alkanes

Propane as Alkylating Agent

Ethane as Alkylating Agent

Methane as Alkylating Agent?

Other Reactions of Light Alkanes

Conclusions

Acknowledgments
Dehydrogenation of Alkanes
Authors: Caspary Karl Josef , Gehrke Helmut , Heinritz‐Adrian Max , Schwefer Meinhard
Published: March 2008

The sections in this article are

Introduction

Importance of Light Alkenes

Historical Developments

Conceptual Approach

Influence of Temperature on the Equilibrium

Influence of Partial Pressure on the Equilibrium

Energy of Alkane Dehydrogenation

Formation of By‐Products

Removal of Hydrogen to Shift the Equilibrium

Spatial Separation of Dehydrogenation and Hydrogen Combustion

Dehydrogenation and Hydrogen Combustion in a Catalyst Bed

Oxidative Dehydrogenation (
ODH
)

Catalytic Systems

Supported Chromia Catalysts

Chromia on
Al
2
O
3
Supports

A
Structure and Reactivity

B
Oxidized State

C
Reduced State

D
Regeneration

Chromia on
Si
O
2
/
Zr
O
2
Supports

Supported Platinum/Tin Catalysts

Platinum as Active Component

Tin as Modifier

State and Mode of Operation of Platinum and Tin

A
State of
Pt
and
Sn

B
Mode of Operation of
Pt
and
Sn

C
Ensemble Effect

D
Ligand Effect

Role of the Support

Regeneration of Supported Platinum/Tin Catalysts

A
Treatment with Molecular Oxygen

B
Treatment with Chlorine

C
Treatment with Hydrogen

Kinetics and Mechanism

Kinetics of Dehydrogenation

Chromia/Alumina Catalysts

A
Mechanism 1

B
Mechanism 2

Platinum and Platinum/Tin Catalysts

Kinetics of Deactivation

Reactor Concepts

Endothermic Character

Preheating the Feed and Carrying out the Reaction in an Adiabatic Reaction System

Carrying Out the Reaction in a Heated Reactor

Preheating the Catalyst and Carrying Out the Reaction in an Adiabatic Reactor

Regeneration

Continuous Systems

Discontinuous Systems

Commercial Processes

UOP
Oleflex Process

U
hde
STAR
Process

ABB
Lummus
CATOFIN
Process

Linde
PDH
Process

S
namprogetti‐
Y
arsintez
FBD
Process

Dehydrogenation of Other Alkanes

Dehydrogenation of Heavy
n
‐Alkanes

Dehydrogenation of Cyclohexane

Future Developments

Membrane Technology

CO
2
as a Diluent

Conclusions and Future Prospects
Dehydrogenation of Ethylbenzene
Authors: Kochloefl Karl , Muhler Martin
Published: March 2008

The sections in this article are

Introduction

Thermodynamics

By‐Products

Effects of Diluents, Especially Steam

Catalysts

Development ofEDBHCatalysts

Role of Potassium

Dehydrogenation of Ethylbenzene on Well‐Defined Iron Oxide Model Catalysts

Deactivation ofKFeCatalysts

Promoters ofKFeCatalysts

Kinetics

Application of Membrane Reactors

Dehydrogenation of Ethylbenzene‐Related Hydrocarbons

Alternative Routes for the Production of Styrene

Industrial Processes and Commercial Catalysts

AdiabaticEBDH

IsothermalEBDH

SMARTEBDHProcess
Metathesis of Alkenes
Authors: Mol Johannes C. , van Leeuwen Piet W. N. M.
Published: March 2008

The sections in this article are

Introduction

Scope of the Reaction

Acyclic Alkenes

Alkadienes

Cyclic Alkenes

Ring‐Opening Metathesis

Metathesis Catalysts

Solid Metathesis Catalysts

Mechanism

Molybdenum Catalysts

MoO3/Al2O3

Effect of Impurities

MoO3/SiO2

Tungsten Catalysts

WO3/Al2O3

WO3/SiO2

Rhenium

Re2O7/Al2O3

ACatalyst Characterization

BParticle Size

CCatalytic Activity

DSelectivity

ModifiedRe2O7/Al2O3Catalysts

ARole of the Promoter

BCatalyst Deactivation

Kinetics

Industrial Applications

ThePhillipsTriolefin Process

The Meta‐4 Process

Production of 1‐Hexene

Production of Neohexene

SHOP

Production of Fine Chemicals

Conclusions
Selective Hydrogenation of Hydrocarbons
Authors: Arnold Heiko , Döbert Frank , Gaube Johann
Published: March 2008

The sections in this article are

Introduction

Kinetics and Mechanisms of Selective Hydrogenation of Dienes

General Aspects of Hydrogenation and Isomerization of Unsaturated Hydrocarbons

Hydrogenation of 1,3‐Butadiene and 1,3‐Cyclooctadiene

Hydrogenation of 1,2‐Butadiene, Cyclopentadiene and Isoprene

Selective Hydrogenation of 1,5,9‐Cyclododecatriene to Cyclododecene

Hydrogenation of Ethyne and Other Alkynes

Effect of Carbon Monoxide in Selective Hydrogenation

Catalysts for Selective Hydrogenation

General Aspects of Catalyst Selection

Comparison ofPdandPtCatalysts

Particle Size Effect

Role of Mass Transfer in Selective Hydrogenation

Gas‐Phase Hydrogenation

Liquid‐Phase Hydrogenation

Partial Hydrogenation of Benzene to Cyclohexene

Selective Hydrogenation Processes in the Downstream Treatment of Naphtha Cracking
Regioselective Hydrogenations
Authors: Claus Peter , Önal Yücel
Published: March 2008

The sections in this article are

Generalities in Regioselectivity with Heterogeneous Catalysts

Definitions

General Factors Determining Selectivity

Reaction Engineering and Selectivity

Selective Hydrogenation of α, β‐Unsaturated Aldehydes

Physicochemical Basics and Reaction Mechanism

Metal Specificity and Structure Sensitivity

Influence of Support Materials, Zeolites and Surface Modifiers

Influence of a Second Metal on Selectivity

Regioselective Hydrogenation in the Presence of Green Solvents

Kinetic Modeling

Selective Hydrogenation of Polyenes

Selective Hydrogenation of Ketones

Selective Hydrogenation of Polycyclic Aromatics and Derivatives

Selective Hydrogenation of Nitroaromatics
Fundamentals of Hydrocarbon Oxidation
Authors: Haber Jerzy
Published: March 2008

The sections in this article are

Introduction

Oxidation Reactions in the Liquid and Gas Phases

Activation of the Hydrocarbon Molecule

Nucleophilic and Electrophilic Oxidation

Selectivity in Hydrocarbon Oxidation

Oxidative Dehydrogenation of Alkanes

Oxidative Dehydrogenation and Oxidation of Alkenes

Reaction Mechanism

Activation of the Hydrocarbon Molecule

Addition of Nucleophilic Oxygen

Oxidative Dehydrogenation of Alkylaromatics

Selective Oxidation of Aromatic Hydrocarbons

Introduction

Oxidation of Benzene to Maleic Anhydride

Oxidation of

o

‐Xylene to Phthalic Anhydride

Oxidation of Butane to Maleic Anhydride

Structure Sensitivity of Oxidation Reactions

Monolayer Oxide Catalysts

Dynamics of Oxide Surfaces in Oxidation Reactions
Oxidative Dehydrogenation of Alkanes
Authors: Håkonsen Silje Fosse , Holmen Anders
Published: March 2008

The sections in this article are

Introduction

Theory

Catalytic Systems forODHof Alkanes

Alkaline Earth Metal Oxide‐Based Catalysts

Transition Metal Oxide‐Based Catalysts

Rare Earth Metal Oxide‐Based Catalysts

Perovskite‐Type and Related Oxides

ODHon Noble Metals at Short Contact Times

Other Catalysts

ODHof Alkanes in Membrane Reactors

Inert Membrane Reactors

Catalytic Membrane Reactors

ODHusing Other Oxidants thanO2

Conclusions and Future Prospects

Acknowledgments
Oxyfunctionalization of Alkyl Aromatics
Authors: Rosowski Frank , Storck Sebastian , Zühlke Jürgen
Published: March 2008

The sections in this article are

Introduction

Production of Terephthalic Acid or Dimethylterephthalate

Production of Phthalic Anhydride

Catalysts for the Production of Phthalic Anhydride

Reaction Conditions, Reactor and Finishing Reactor of thePA‐Synthesis

Reaction Mechanism ofPASynthesis

Production of Benzoic Acid or Benzaldehyde

General Remarks

Gas‐Phase Oxidation of Toluene to Benzoic Acid and Benzaldehyde

Oxidation ofp‐Xylene to Terephthaldehyde andp‐Toluic Aldehyde

Conclusions
Direct Ring Oxidation of Aromatics to Phenols
Authors: Klemm Elias , Reitzmann Andreas , Vogel Bernd
Published: March 2008

The sections in this article are

Conventional Production of Phenols

Fundamentals of Direct Ring Oxidation

Molecular Oxygen

Molecular Oxygen and the Presence of a Reductant

Hydrogen Peroxide

Nitrous Oxide

Direct Ring Oxidation of Benzene to Phenol

Molecular Oxygen

AGas Phase

BLiquid Phase

Molecular Oxygen and the Presence of a Reductant

AGas Phase

BLiquid Phase

Nitrous Oxide

AGas Phase

BLiquid Phase

Hydrogen Peroxide

AGas Phase

BLiquid Phase

Direct Ring Oxidation of Substituted Aromatics

Hydroxylation of Phenol

AHydrogen Peroxide

BNitrous Oxide

CMolecular Oxygen

Hydroxylation of Toluene

AHydrogen Peroxide

BNitrous Oxide

CMolecular Oxygen

Hydroxylation of Benzonitrile

AHydrogen Peroxide

BNitrous Oxide

Concluding Remarks
Diastereoselective Catalysis
Authors: Besson Michèle , Pinel Catherine
Published: March 2008

The sections in this article are

Introduction

Diastereoselective Hydrogenation of
C

C
Bonds

Synthesis of Amino Acid Derivatives

Synthesis of Building Blocks

Diastereoselective Hydrogenation of
C

O
Bonds

Diastereoselective Hydrogenation of
C

N
Bonds

Hydrogenation of Imines

Hydrogenation of Oximes and Hydrazones

Diastereoselective Hydrogenation of Aromatic Rings

Diastereoselective Hydrogenation of Nitrogen‐Containing Rings

Pyridine Derivatives

Pyrazine Derivatives

Pyrrole Derivatives

Furan and Benzofuran Derivatives

In‐Situ
Diastereoselective Hydrogenation

Conclusions
W
acker Chemistry with Solid Catalysts
Authors: Jacobs Pierre A.
Published: March 2008

The sections in this article are

The Overall
W
acker Cycle

Industrial Production of Acetaldehyde via
W
acker Chemistry

Related Chemistry

Mechanistic Aspects of
W
acker Chemistry

Heterogeneous
W
acker Chemistry on Zeolites

Combined
Pd
and
V
as Wacker Elements in Heteropolyanion Catalysts

Pd
/
Cu
and
Pd
/
V
Couples in Solid
W
acker Catalysts

Conclusions

Acknowledgments
Universal Colorimetric Detection of Nucleic Acids Based on Polydiacetylene (PDA) Liposomes
Authors: Jung Yun Kyung , Kim Tae Won , Kim Jumi , Kim Jong‐Man , Park Hyun Gyu
Published: March 2008

A universal colorimetric method for the detection of nucleic acids, based on ionic interactions by polydiacetylene (PDA) liposomes, is described. Primary and quaternary amine‐modified diacetylene monomers were synthesized and used to generate positively charged PDA liposomes. The resulting PDA sensors showed a dramatic color change from blue to red upon the addition of nucleic acids amplified by using the polymerase chain reaction (PCR) due to the stimuli caused by ionic interactions between the positively charged PDA and negatively charged phosphate backbone of the nucleic acids. The color change that takes place can be simply detected by the naked eye. Compared with quaternary amine‐functionalized PDA vesicles, the primary amine‐functionalized PDA underwent a more intense color transition under optimized conditions. By using the PDA‐based colorimetric sensor, nucleic acids amplified by common PCR reaction, whose typical concentration is around 100 nM, can be readily detected. Since implementation of this universal colorimetric method is simple, rapid and does not require any sophisticated instrumentation, it should have greatly enhanced applications as a technology for DNA diagnosis.
Synthesis of Rhodium Colloidal Nano‐Coating Grafted Mesoporous Silica Composite and its Application as Efficient Environmentally Benign Catalyst for Heck‐Type Reaction of Arylboronic Acids
Authors: Li Liang , Shi Jianlin
Published: March 2008

The synthesis and characterization of rhodium colloidal layer grafted mesoporous SBA‐15 material, designated as SBA‐Rh, are presented. In the preparation of this new catalyst, SBA‐15 mesoporous material was used as support without any pretreatment. The SiH functional groups were introduced onto the surface which resulted in highly dispersed metal colloid layer both on the outer and inner surface of the supporting material. The material was investigated for Heck‐type coupling reactions of alkenes with ayboronic in organic/water solvent. The ultrahigh specific area, large pore opening, and highly dispersed catalyst species in SBA‐Rh material created one of the most active heterogeneous catalysts for such reactions. Rhodium element was not detected in the final mixture by ICP after reaction. The catalyst species showed very high stability against leaching from the matrix and can be recycled for repeated use.
Mechanistic study on dimerization of acetylene with a Nieuwland catalyst
Authors: Tachiyama Takashi , Yoshida Makoto , Aoyagi Tatsuhiro , Fukuzumi Shunichi
Published: March 2008

A mechanistic study on the Nieuwland catalysis for dimerization of acetylene is performed by detecting copper–acetylene and copper–monovinylacetylene π‐complexes and also by examining the kinetics under virtually the same reaction conditions employed in the industrial process. An efficient H/D exchange occurs between acetylene and protons in the Nieuwland catalytic system. Addition of a coordinating ligand to the conventional Nieuwland catalytic system results in improvement of the catalytic activity and selectivity for the acetylene dimerization. The kinetic analysis including the kinetic deuterium isotope effect provides valuable insight into the Nieuwland catalytic mechanism of the dimerization of acetylene. Copyright © 2008 John Wiley & Sons, Ltd.
Water‐soluble 2‐arylnaphthoxazole‐derived palladium (II) complexes as phosphine‐free catalysts for the Suzuki reaction in aqueous solvent
Authors: Li Hong , Wu Yangjie
Published: March 2008

Two water‐soluble palladium (II) complexes 2 and 4 have been synthesized from easily available 2‐arylnaphthoxazole derivatives. They were successfully applied to the Suzuki coupling of aryl bromides with phenylboronic acid in water at 100 °C under phosphine‐free conditions. Copyright © 2008 John Wiley & Sons, Ltd.