Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis

化学 催化作用 金属有机骨架 滴定法 密度泛函理论 物理化学 光化学 高分子化学 有机化学 计算化学 吸附
作者
Benjamin Yeh,Saumil Chheda,Steven D. Prinslow,Adam S. Hoffman,Jiyun Hong,Jorge E. Perez-Aguilar,Simon R. Bare,Connie C. Lu,Laura Gagliardi,Aditya Bhan
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:145 (6): 3408-3418 被引量:17
标识
DOI:10.1021/jacs.2c10551
摘要

A mixed-valence oxotrimer metal-organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ∼20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ∼0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ∼62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55-67 kJ mol-1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee-Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. This study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
拼尽全力发布了新的文献求助10
刚刚
舒服的蝴蝶完成签到,获得积分10
1秒前
1秒前
充电宝应助碧蓝的宝马采纳,获得10
2秒前
kelakola完成签到,获得积分10
2秒前
强扭的瓜完成签到 ,获得积分10
2秒前
maomao发布了新的文献求助10
2秒前
柯友卉完成签到 ,获得积分10
2秒前
Janusfaces发布了新的文献求助10
3秒前
啥时候吃火锅完成签到 ,获得积分0
3秒前
孙喆能完成签到,获得积分10
3秒前
充电宝应助刘江涛采纳,获得10
3秒前
4秒前
111发布了新的文献求助10
4秒前
Owen应助刹那的颜色采纳,获得10
4秒前
NexusExplorer应助wsd886采纳,获得10
4秒前
Lynn完成签到,获得积分10
5秒前
仁和完成签到 ,获得积分10
5秒前
6秒前
Tina完成签到,获得积分10
6秒前
王哈哈完成签到,获得积分20
6秒前
8秒前
SciGPT应助科研通管家采纳,获得30
8秒前
quhayley应助科研通管家采纳,获得10
8秒前
香蕉觅云应助科研通管家采纳,获得10
8秒前
情怀应助科研通管家采纳,获得10
8秒前
丘比特应助科研通管家采纳,获得10
9秒前
赘婿应助科研通管家采纳,获得10
9秒前
9秒前
9秒前
SHAO应助科研通管家采纳,获得10
9秒前
Jasper应助科研通管家采纳,获得10
9秒前
March应助科研通管家采纳,获得10
9秒前
赘婿应助科研通管家采纳,获得10
9秒前
fd163c应助科研通管家采纳,获得10
9秒前
SYLH应助科研通管家采纳,获得20
9秒前
脑洞疼应助科研通管家采纳,获得10
9秒前
慕青应助科研通管家采纳,获得10
10秒前
无花果应助科研通管家采纳,获得10
10秒前
quhayley应助科研通管家采纳,获得10
10秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
‘Unruly’ Children: Historical Fieldnotes and Learning Morality in a Taiwan Village (New Departures in Anthropology) 400
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
基于可调谐半导体激光吸收光谱技术泄漏气体检测系统的研究 350
Robot-supported joining of reinforcement textiles with one-sided sewing heads 320
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3988732
求助须知:如何正确求助?哪些是违规求助? 3531027
关于积分的说明 11252281
捐赠科研通 3269732
什么是DOI,文献DOI怎么找? 1804764
邀请新用户注册赠送积分活动 881869
科研通“疑难数据库(出版商)”最低求助积分说明 809021