Larger WOx domains would better disperse the extra electron densities transferred onto the WOx species during the acidic catalytic reaction and, thus, help to stabilize acidic sites in this system. The incorporation of Zr into the WOx structure may further change the electronic structure and enhance the catalytic acidity. Thus, the ~0.8-1nm Zr-WOx mixed-oxide clusters exhibit a greater catalytic activity than the ultra-dispersed species (i.e. poly-tungstate with 2-6 WOx units and mono-tungstate with isolated WOx unit.)

Identification and Design of Super-Active Zr–WOx Nano-Clusters for Solid Acid Catalysis((NSF NIRTNSF NIRT # #06090180609018 ))

Wu ZhouWu Zhou11, Elizabeth I. Ross-Medgaarden, Elizabeth I. Ross-Medgaarden22, William V. Knowles, William V. Knowles33, , Michael S. WongMichael S. Wong33, Israel E. Wachs, Israel E. Wachs22 & Christopher J. Kiely & Christopher J. Kiely11 1 Dept. of Materials Science & Engineering, Lehigh University, Bethlehem, PA 18015.

2 Operando Molecular Spectroscopy & Catalysis Lab, Dept. of Chemical Engineering, Lehigh University, Bethlehem, PA 18015.3 Dept. of Chemical & Biomolecular Engineering, Rice University, Houston, TX 77005.

Electron Microscopy Characterization of WO3/ZrO2 Catalysts → Directly Imaging the Catalytic Active Species

Catalyst Design: To Increase the Number Density of the Catalytic Active Sites and Consequently Improve the Catalyst Performance

SamplesTotal W surface density

(W-atoms/nm2)W-atoms/nm2

addedZr-atoms/nm2

addedActivity †

(normalized)

2.5 WZrO2-723K 2.5 0 0 1*

(3.5W+3.5Zr)/2.5 WZrO2-973K 6.0 3.5 3.5 167

(3.5W)/2.5 WZrO2-973K 6.0 3.5 0 4.8

(3.5Zr)/2.5 WZrO2-973K 2.5 0 3.5 1.7

6.2 WZrOH-973K 6.2 NA NA 118

5.9 WZrO2-723K 5.9 NA NA 2.6

Both ZrOx & WOx Additions

Only WOx Addition

Only ZrOx Addition

Both ZrOx & WOx Additions

Starting Model WO3/ZrO2

Active Catalysts: WO3/ZrOx(OH)4-2x

Denoted: WZrOH, on metastable zirconium oxyhydroxide support

Inactive Model Catalysts: WO3/ZrO2

Denoted: WZrO2, on heat-treated stable Degussa ZrO2 support

Incipient Wetness Impregnation with Ammonium Metatungstate: (NH4)10W12O41*5H2O

Calcination Temperatures: WZrOH : 773-1173K

Model WZrO2 : 723K

Catalyst Activity Testing: Methanol TPSR Spectroscopy → number of exposed surface acid sites

Steady-State Methanol Dehydration → turnover frequency (TOF)

Aberration Corrected Electron Microscopy:

High-Resolution TEM (HRTEM): morphology and crystal structure

High-Angle Annular Dark-Field (HAADF) STEM: atomic structure with Z-contrast

Bulk WO3

3 2WO /ZrO3 2 3 32 CH OH H O + CH OCH (DME)

mono-tungstate(isolated WOx unit)

poly-tungstate(2-D network structure having 2-6 WOx units)

Low activity2.9WZrOH-773KTOF=1.4*10-2 sec-1

5 nm5 nm

High activity6.2WZrOH-1073KTOF=6.9*10-1 sec-1

HRTEM

HRTEM

HAADF HAADF

HAADFHAADF

BF-TEM HAADF

Synthesis, Activity Testing, and Characterizationof WO3/Zirconia Catalysts

A

B

C

Inactive model catalyst

5.9WZrO2-723KTOF=3.1*10-3sec-1

Dominant surface WOx species:

0.8-1nm 3-D Zr-WOx mixed oxide clusters (10-15 inter-linked WOx units) co-exist with mono-tungstate and poly-tungstate.Contrast variation within the clusters suggests possible incorporation of Zr atoms in the WOx cluster structure.

0.8-1nm pure WOx clusters co-exist with mono-tungstate and poly-tungstate.The different activities indicate the clusters in sample B and C have different compositions.

HAADF

B

C

inactive model WO3/ZrO2 catalyst 2.5 WZrO2-723K

(NH4)10

W12O41

impregnation

Zr[OC(CH3)

3]4

impregnation, N2

calcination

973K, 3hpost-impregnated with ZrOx only

(3.5Zr)/2.5 WZrO2-973K

intermediate, post-impregnated with WOx only

calcination973K, 3h

Zr[OC(CH3)3]4

impregnation, N2

calcination973K, 3h

post-impregnated with WOx only(3.5W)/2.5 WZrO2-973K

co-impregnated with both WOx & ZrOx

(3.5W+3.5Zr)/2.5 WZrO2-973K

These post-impregnation experiments demonstrate that both ZrOx and WOx in an intimately mixed form are crucial in forming the catalytically active sites. The formation of mixed Zr-WOx clusters via co-impregnation of both ZrOx and WOx significantly increase the catalytic acidity of the original inactive model catalyst, and make it comparable to the most active WZrOH-type materials. In contrast, post-impregnation of the ZrOx precursor or WOx precursor alone shows only a minimal improvement in catalytic activity.

The starting low activity 2.5WZrO2 model catalyst exclusively shows highly dispersed surface mono- and poly-tungstate species.

Post-impregnation with ZrOx alone results in a catalyst displaying only surface mono- and poly-tungstate species; no clusters were formed and the apparent WOx surface coverage was comparable to that of the starting material.

Post-impregnation with additional WOx precursor generates an additional population of 0.8-1nm WOx clusters.

Co-impregnation with both WOx and ZrOx produces a high density population of sub-nm oxide clusters, and intensity variations in HAADF images indicate the successful inclusion of Zr atoms in the WOx clusters.

• 0.8-1nm mixed Zr-WOx clusters constitute the most catalytic active species in the WO3/ZrO2 catalyst system.

• The precise role of the small amount of incorporated ZrOx species will be investigated with first-principle calculations informed by direct structure observations from aberration-corrected STEM-HAADF imaging.

Important Temperatures:• Tammann temperature of ZrO2 (1494K) > calcination temperature (973K): unlikely for Zr-species to diffuse from the bulk ZrO2 crystal into the surface WOx clusters.

• Hüttig temperature of ZrO2 (896K) < calcination temperature (973K): the surface ZrOx species (from post-impregnated ZrOx precursor) have sufficient surface mobility to agglomerate and become intermixed with surface WOx species and incorporated into the sub-nm clusters.

* TOF = 1.2 ×10-3 s-1.

References:[1] Ross-Medgaarden et al. J. Catal. 256, 108-125 (2008)[2] Zhou et al. Nat. Chem. DOI: 10.1038/NCHEM.433 (2009)

Intensity Profiles

Table 1 | Steady-state turnover frequency (TOF) values for the methanol dehydration to DME reaction at 573K.