The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst

被引：130

作者：

Amann, Peter ^{[1
,6
]}

Kloetzer, Bernhard ^{[2
]}

Degerman, David ^{[1
]}

Koepfle, Norbert ^{[2
,7
]}

Goetsch, Thomas ^{[3
]}

Loemker, Patrick ^{[1
,4
]}

Rameshan, Christoph ^{[5
]}

Ploner, Kevin ^{[2
]}

Bikaljevic, Djuro ^{[2
]}

Wang, Hsin-Yi ^{[1
]}

Soldemo, Markus ^{[1
,8
]}

Shipilin, Mikhail ^{[1
]}

Goodwin, Christopher M. ^{[1
]}

Gladh, Joergen ^{[1
,8
]}

Stenlid, Joakim Halldin ^{[1
,9
]}

Boerner, Mia ^{[1
]}

Schlueter, Christoph ^{[4
]}

Nilsson, Anders ^{[1
]}

机构：

[1] Stockholm Univ, AlbaNova Univ Ctr, Dept Phys, S-10691 Stockholm, Sweden

[2] Univ Innsbruck, Inst Phys Chem, Innrain 52c, A-6020 Innsbruck, Austria

[3] Max Planck Gesell, Dept Inorgan Chem, Fritz Haber Inst, Faradayweg 4-6, D-14195 Berlin, Germany

[4] DESY, Photon Sci, Notkestr 85, D-22607 Hamburg, Germany

[5] Tech Univ Wien, Inst Mat Chem, Getreidemarkt 9-BC-01, A-1060 Vienna, Austria

[6] Scienta Omicron AB, Danmarksgatan 22, S-75323 Uppsala, Sweden

[7] Plansee SE, Metallwerk Planseestr 71, A-6600 Reutte, Austria

[8] PULSE Inst, SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA

[9] SUNCAT Ctr Interface Sci & Catalysis, SLAC Natl Accelerator Lab, 2575 Sand Hill Rd, Menlo Pk, CA 94025 USA

来源：

SCIENCE | 2022年 / 376卷 / 6593期

基金：

瑞典研究理事会;

关键词：

ACTIVE-SITE; PHOTOELECTRON-SPECTROSCOPY; HYDROGEN-PRODUCTION; CO2; HYDROGENATION; ALPHA-BRASS; CORE-LEVEL; CU; SURFACE; COPPER; ZNO;

D O I：

10.1126/science.abj7747

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO2/CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO2 methanol synthesis..

引用

页码：603 / +

页数：78

共 50 条

[31] Effects of Al3+ precipitation onto primitive amorphous Cu-Zn precipitate on methanol synthesis over Cu/ZnO/Al2O3 catalyst
Cheonwoo Jeong
Jongha Park
Jinsung Kim
Joon Hyun Baik
Young-Woong Suh
Korean Journal of Chemical Engineering, 2019, 36 : 191 - 196
[32] Effective hydrogenation of carbonates to produce methanol over a ternary Cu/Zn/Al catalyst
Li, Jiachen
Wang, Liguo
Hui, Xiang
Zhang, Chanjuan
Cao, Yan
Xu, Shuang
He, Peng
Li, Huiquan
RSC ADVANCES, 2020, 10 (22) : 13083 - 13094
[33] Effects of Al3+ precipitation onto primitive amorphous Cu-Zn precipitate on methanol synthesis over Cu/ZnO/Al2O3 catalyst
Jeong, Cheonwoo
Park, Jongha
Kim, Jinsung
Baik, Joon Hyun
Suh, Young-Woong
KOREAN JOURNAL OF CHEMICAL ENGINEERING, 2019, 36 (02) : 191 - 196
[34] Methanol synthesis revisited: The nature of the active site of Cu in industrial Cu/ZnO/Al2O3 catalyst and Cu-Zn synergy
Gogate, Makarand R.
PETROLEUM SCIENCE AND TECHNOLOGY, 2019, 37 (06) : 671 - 678
[35] Copper-Zinc Alloy-Free Synthesis of Methanol from Carbon Dioxide over Cu/ZnO/Faujasite
Zabilskiy, Maxim
Sushkevich, Vitaly L.
Newton, Mark A.
van Bokhoven, Jeroen A.
ACS CATALYSIS, 2020, 10 (23) : 14240 - 14244
[36] ROLE OF ZNO IN PROMOTING METHANOL SYNTHESIS OVER A PHYSICALLY-MIXED CU/SIO2 AND ZNO/SIO2 CATALYST
KANAI, Y
WATANABE, T
FUJITANI, T
SAITO, M
NAKAMURA, J
UCHIJIMA, T
ENERGY CONVERSION AND MANAGEMENT, 1995, 36 (6-9) : 649 - 652
[37] Liquid catalyst interactions in slurry reactors:: methanol synthesis over zinc chromite
Roberts, GW
Márquez, MA
Haney, CA
APPLIED CATALYSIS A-GENERAL, 1999, 183 (02) : 395 - 410
[38] Unravelling the Zn-Cu Interaction during Activation of a Zn-promoted Cu/MgO Model Methanol Catalyst
Pandit, Lakshmi
Boubnov, Alexey
Behrendt, Gereon
Mockenhaupt, Benjamin
Chowdhury, Chandra
Jelic, Jelena
Hansen, Anna-Lena
Saraci, Erisa
Ras, Erik-Jan
Behrens, Malte
Studt, Felix
Grunwaldt, Jan-Dierk
CHEMCATCHEM, 2021, 13 (19) : 4120 - 4132
[39] METHANOL SYNTHESIS ON A CU(100) CATALYST
SZANYI, J
GOODMAN, DW
CATALYSIS LETTERS, 1991, 10 (5-6) : 383 - 390
[40] The role of ZnO in Cu/ZnO methanol synthesis catalysts
Nakamura, J
Uchijima, T
Kanai, Y
Fujitani, T
CATALYSIS TODAY, 1996, 28 (03) : 223 - 230

← 1 2 3 4 5 →