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N14 June 1995, p. 51. Simon, a business pro- fessor at the University of Maryland has challenged others to name ‘any trend per- taining to human welfare’ and to place a wager as to whether that trend would get worse over time. Two scientists have re- sponded, but as yet it has not been agreed as to whether the trends suggested will be acceptable for the wager. The two scien- tists, when told that these topics might not be acceptable to Simon, responded that he could take it or leave it, adding ‘Frankly, astronomers don’ t spend their time debat- ing with flat-earthers, and evolutionists don’ t spend their time debating with cre- ationists.’ This displays the root of the problem, since it is precisely these types of debate that are needed if our science is to move forward. So although the answer to the title ques- tion is that catalysis is difficult, we must persevere and get it right. It is too important to society for us to fail. What is required is the correct focusing of our efforts and fundings, if we aim to succeed. We need new catalysts and processes and, al- though these will come by detailed step- wise increments in our knowledge base, we also need the massive step changes in technologies. In the UK, the Technology Foresight review identified low-tempera- ture CH4 oxidation as a key goal. A number of us have known this for a long time and have tried, but, apart from the many publi- cations, there has not yet been much to show. However, nature got there millions of years ago, since the room temperature activation of CHI is an everyday occur- rence for methylmonooxygenese. Nature shows us that we have a lot to learn, but nature also gives us a clue - it can be done. The knowledge that a target is achievable is a big help. Of course we have had help from thermodynamics for many years now that can tell us when a specific target is impossible, e.g. perpetual motion. This could have helped some people who were caught up in a wager on this topic at the beginning of the nineteenth century, since lack of knowledge can be very costly: “Mr. Gobert of Philadelphia, who lately advertised that he would take any bet from five to one hundred thousand dollar on the feasibility of Mr. Redheffer’s discovery of perpetual motion, was taken up for five thousand dollars, by Mr. Jacob Perkins of Newburyport. After making a series of ex- periments in vain, to construct a moving machine upon Mr. Redheffer’s self moving principle, he discovered to his infinite cha- grin, that Mr. Redheffer had in the mean- time moved himself off, with 20,000 dollars in notes of hand given him by Mr. Gobert for his valuable secret. We understand that Mr. Gobert has acknowledged his bet for- feited, and is now in pursuit of Redheffer, who keeps himself in perpetual motion to elude him. I1 (Weekly Register, 1813) GRAHAM HUTCHINGS Mesoporous and Microporous Materials: Recent Advances Zeolite p has recently become a fashionable zeolite for study. For a long time zeolite ,!? was eclipsed by the sub- sequent development of the zeolite ZSM-5 as the wonder catalyst of the 1970’s and 1980’s, but zeolitefi is now finding potential uses in a number of processes. Pan of the interest lies in the structure of zeolite p since one of the polymorphs can poten- tially exist in a chiral form. Recently, Paul applied catalysis A: General Volume 129 No. 2 - 31 August 1995

Mesoporous and microporous materials: Recent advances

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Page 1: Mesoporous and microporous materials: Recent advances

N14

June 1995, p. 51. Simon, a business pro- fessor at the University of Maryland has challenged others to name ‘any trend per- taining to human welfare’ and to place a wager as to whether that trend would get worse over time. Two scientists have re- sponded, but as yet it has not been agreed as to whether the trends suggested will be acceptable for the wager. The two scien- tists, when told that these topics might not be acceptable to Simon, responded that he could take it or leave it, adding ‘Frankly, astronomers don’t spend their time debat- ing with flat-earthers, and evolutionists don’t spend their time debating with cre- ationists.’ This displays the root of the problem, since it is precisely these types of debate that are needed if our science is to move forward.

So although the answer to the title ques- tion is that catalysis is difficult, we must persevere and get it right. It is too important to society for us to fail. What is required is the correct focusing of our efforts and fundings, if we aim to succeed. We need new catalysts and processes and, al- though these will come by detailed step- wise increments in our knowledge base, we also need the massive step changes in technologies. In the UK, the Technology Foresight review identified low-tempera- ture CH4 oxidation as a key goal. A number of us have known this for a long time and have tried, but, apart from the many publi- cations, there has not yet been much to show. However, nature got there millions of years ago, since the room temperature activation of CHI is an everyday occur- rence for methylmonooxygenese. Nature shows us that we have a lot to learn, but nature also gives us a clue - it can be done. The knowledge that a target is achievable is a big help. Of course we have

had help from thermodynamics for many years now that can tell us when a specific target is impossible, e.g. perpetual motion. This could have helped some people who were caught up in a wager on this topic at the beginning of the nineteenth century, since lack of knowledge can be very costly:

“Mr. Gobert of Philadelphia, who lately advertised that he would take any bet from

five to one hundred thousand dollar on the feasibility of Mr. Redheffer’s discovery of perpetual motion, was taken up for five thousand dollars, by Mr. Jacob Perkins of Newburyport. After making a series of ex- periments in vain, to construct a moving machine upon Mr. Redheffer’s self moving principle, he discovered to his infinite cha- grin, that Mr. Redheffer had in the mean-

time moved himself off, with 20,000 dollars in notes of hand given him by Mr. Gobert

for his valuable secret. We understand that Mr. Gobert has acknowledged his bet for- feited, and is now in pursuit of Redheffer, who keeps himself in perpetual motion to elude him. I1 (Weekly Register, 1813)

GRAHAM HUTCHINGS

Mesoporous and Microporous Materials: Recent Advances

Zeolite p has recently become a fashionable zeolite for study. For a long time zeolite ,!? was eclipsed by the sub- sequent development of the zeolite ZSM-5 as the wonder catalyst of the 1970’s and 1980’s, but zeolitefi is now finding potential uses in a number of processes. Pan of the interest lies in the structure of zeolite p since one of the polymorphs can poten- tially exist in a chiral form. Recently, Paul

applied catalysis A: General Volume 129 No. 2 - 31 August 1995

Page 2: Mesoporous and microporous materials: Recent advances

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Cox at Portsmouth, UK has postulated a mechanism for faulting in zeolite b [A.P. Stevens and Paul A. Cox, J. Chem. Sot., Chem. Commun., (1995) 3431. They have used molecular modelling, based on the Biosym software, to predict the locations and orientations adopted by the 1 ,l-di- benzyl-1 ,l -dimethylammonium template cations to the zeolite. They have then used this to rationalise the vast array of data available for zeolite B concerning crystal- lographic faulting.

Another material that has received con- siderable attention is structured meso- porous MCM41. One problem associated with this material is that, unlike zeolites, the long range order of the mesoporous struc- ture is not usually significant. An attempt has been made to overcome this problem by Ryoo and Kim [J. Chem. Sot., Chem. Commun., (1995) 7111, who have used powder X-ray diffraction, “Si and “‘Xe NMR spectroscopy to study this problem. They have shown that long range structural order and textured uniformity can be signi- ficantly improved when acetic acid is added repeatedly during the preparation. The authors attribute the effect to a shift in the reaction equilibrium of the crystal- lisation process.

A novel use of MCM41 as a catalyst for acid and base catalyzed reactions is de- scribed by Kloestra and Van Bekkum [J. Chem. Sot., Chem. Commun., (1995) 10051. They have used the caesium and sodium form of MCM-41 and have shown that these are selective, water stable and recyclable catalysts for the base-catalyzed Knoevanagel condensation and the acid- catalyzed acetalisation and alcohol con- densation. However, MCM-41, when im- pregnated with caesium acetate, was shown to act as a base catalyst for the

Michael addition reaction. This demonstra- tion of reaction flexibility indicates that MCM41 will have as extensive reaction chemistry as its microporous analogues and this should promote further research in this interesting area.

One major development, awaited for some time by many, has now been an- nounced. This involves the enhancement in activity of VPI-5 for acid catalyzed reac- tion. Groups in Spain [S. del Val, J. Blasco, E. Sastre and J. Perez-Pariente, J. Chem. Sot., Chem. Commun., (1995) 7311 have found a novel method to introduce Si into VPI-5 and have synthesised the silicon- substituted material. They have shown its use for the acid catalyzed m-xylene isomerisation and disproportionation reac- tions However, the substitution does not appear to have improved the chemical sta- bility of this material since it still is prone to structure collapse on heating.

GRAHAM J. HUTCHINGS

Water-gas Shift Reaction Studies: A Further Exploration of Controversy?

Water-gas shift reaction chemistry has been well studied and the author has re- cently reviewed a large amount of the ex- perimental evidence for this reaction [see Rhodes et al., Catal. Today, 23 (1995) 431. Two recent papers are quite thought pro- voking.

Work reported from the group of Camp- bell [J. Yoshirhara, S.C. Parker, A. Schafer and C.T. Campbell, Catal. Lett., 31 (1995) 3131 concerns both the reverse water-gas shift reaction and the related methanol syn- thesis over clean polycrystalline copper. They report a detailed kinetics study for the simultaneous reactions and report an ab-

applied catalysis A: General Volume 129 No. 2 - 31 August 1995