Lemma 1: If continuous function $f$ has extreme points, then $\exists x,y,~f(x)=f(y)$.
Proof. Without loss of generality, we assume $f$ has a local maximum point at $t$. According to the definition of local maximum, we have $$\exists \xi>0, \forall x\in\underset{o}{U}(t,\xi), f(x) \leq f(t)$$Let $$M = \max\left\{\min_{x\in(t-\xi, t)}f(x), \min_{x\in(t,t+\xi)}f(x)\right\}$$
By Intermediate Value Theorem, there is function value $(M+f(t))/2$ in both intervals $(t-\xi, t)$ and $(t,t+\xi)$.$\Box$
Lemma 2: If $f$ is continuous in $\mathbb{R}$ and satisfies $\forall x,y, ~f(x)\neq f(y)$, then $f$ is strictly monotone.
Proof. Suppose $f$ is not strictly monotone. Because $\forall x,y, ~f(x)\neq f(y)$, we have $\exists a< b,~f(a)< f(b)$. Let
$$\begin{align*}H = \sup_{t>a} \{\forall x\in(a,t), f(x)<f(t)\}\end{align*}\\ L = \inf_{t< a} \{\forall x\in(t,a), f(t)<f(x)\}$$
If $H\to\infty$,$L\to-\infty$, then $f$ is strictly monotone, which contradicts the assumption. So there should be one of them $\nrightarrow \infty$.
Without loss of generality, we assume it is $H$ that $\nrightarrow \infty$, then $\exists \xi, \forall x\in\underset{o}{U}(H,\xi), f(x) < f(H)$ (see the definition of $H$), which indicates that $H$ is a local maximum. According to Lemma 1, $\exists x,y,~f(x)=f(y)$. Contradiction occrus, so $f$ must be strictly monotone.$\Box$
Lemma 3: If $f'$ is strictly monotone and differentiable in $\mathbb{R}$, then $f$ is unbounded.
Proof. $f''>0$ or $f''<0$ since $f'$ is strictly monotone and differentiable . The second-order Taylor series of $f$ is:
$$f(x) = f(0) + f'(0)x + f''(\xi)x^2$$
So $f$ is unbounded.$\Box$
Theorem: If $f$ is bounded and twice differentiable in $\mathbb{R}$, then $\exists \xi, f''(\xi)=0$
Proof. $f$ is twice differentiable, so $f'$ is differentiable. Suppose $\forall x,y, ~f'(x)\neq f'(y)$, then $f'$ is strictly monotone (Lemma 2), and $f$ is bounded (Lemma 3), so the assumption doesn't hold, that means $\exists x,y,~f'(x)=f'(y)$.
According to Mean Value Theorem, $\exists \xi, f''(\xi)=0$.$\Box$